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Cavani, who struck a brace against Manchester City to eliminate the Premier League leaders in the group stages, was again in inspirational form as he raced past a ball-watching Branislav Ivanovic and gave Napoli the lead at half-time, before setting up Lavezzi's second in the 65th minute.
Lavezzi had earlier scored with a curling shot to equalize after Juan Mata gave Chelsea a surprise lead following a mistake by Napoli captain Paolo Cannavaro.
This was Chelsea's fifth match without a win and means there is likely to be no English team in the quarter-finals after Arsenal lost 4-0 at AC Milan last week.
Only three teams have come back from two goals down in a second leg.
"I want to be the fourth," Chelsea coach Andre Villas-Boas said. "We're sure we can turn it around at the Bridge because of the chances we had tonight. Being clinical in front of the goal was the difference between the two teams. Napoli were efficient in front of goal and we weren't. We made a couple of mistakes and Napoli took advantage of those opportunities."
Chelsea, who have slipped to fifth in the Premier League, were without captain John Terry, and the club announced before kick-off that the defender needs knee surgery and will be out for up to six weeks. Terry's absence told as Napoli breached the Chelsea defence time and time again.
"We have to focus on reorganizing the relationship between the back four," Villas-Boas said. "We have to solve these issues at the back so we can profit more from the opportunities we have. ... The first two goals we had more numbers back, and if we were more organized, they wouldn't have scored."
It could have been even worse for Chelsea as Napoli wasted several opportunities to extend their advantage, most notably when Ashley Cole cleared Christian Maggio's close-range shot off the line.
"It is a pity that we didn't get the fourth, with Maggio's chance," Napoli coach Walter Mazzarri said. "That would have helped us and we would have been more calm going to London. Chelsea were strong, as we knew they'd be. We were great, especially up front and in reacting to Chelsea going ahead. We had a difficult 15 minutes but then we equalized and grew from there."
"Napoli had great chances tonight but it won't be easy in London. Chelsea are capable of scoring two goals at home so we have to take our opportunities. There's the great disappointment not to have scored a fourth, we had so many chances to and we deserved to."
Napoli got off to a bright start and could have taken an early lead but Lavezzi miscontrolled a good through ball from Gokhan Inler and Petr Cech gathered the danger.
Having started the game ahead of Cole due to the England man’s fitness concerns, Bosingwa was forced off with an apparent hamstring injury just over 10 minutes into the proceedings, prompting the first-choice left-back’s introduction.
As Napoli pressed, a mistake allowed Florent Malouda to rob the ball and race toward goal, but Cannavaro made a perfectly timed tackle just as the Chelsea striker was about to shoot.
The home side almost went in front in the ninth minute when Marek Hamsik picked out a completely unmarked Cavani on the left of the area. Cavani has scored three goals in his last two Serie A games to take his tally to 15, but the Uruguayan was denied by a great leg save from Cech.
Napoli were looking more and more dangerous and seemed certain to take the lead but Chelsea gave an early warning that they were not to be ignored when a long throw from Cech to Malouda caught the Napoli defence napping and goalkeeper Morgan De Sanctis did well to clear.
However, it was mainly one-way traffic and Christian Maggio saw a fierce cross-goal shot kept out by another impressive Cech dive.
Chelsea stunned the Stadio San Paolo crowd in the 27th minute when Cannavaro gifted the visitors the lead by diverting a cross straight into Mata's path. After being picked out by Didier Drogba, Daniel Sturridge's resulting cross was inexplicably mis-kicked by the Napoli captain back toward his own goal. The ball fell perfectly for Mata, and the Spaniard calmly slotted the ball into the left corner.
The Premier League side almost doubled their lead but David Luiz headed Mata's corner narrowly over.
Napoli drew level in the 38th when Lavezzi collected the ball on the edge of the area, eluded Chelsea midfielder Raul Meireles, before curling it into the bottom right corner past Cech's outstretched hand.
Ramires had a great chance to restore Chelsea's advantage moments later but he blazed his effort well over.
Chelsea were to regret that missed opportunity as Cavani put Napoli in front on the stroke of half-time, bundling home Inler's cross from almost on the goalline for his fifth goal in seven Champions League appearances this season.
"We had a chance to go 2-0 up and a couple of defensive mistakes that against Napoli, with their attacking strength, will get punished," Villas-Boas said.
The visitors almost drew level immediately after the break but Hamsik cleared off the line following a scramble in the Napoli area.
Napoli should have extended their advantage when the ever-dangerous Cavani raced down the right flank before releasing Walter Gargano for what looked to be a certain third goal but, one on one with the goalkeeper, he fired narrowly wide of the right upright.
Chelsea improved as the match went on and came close to the equalizer on several occasions, notably when Didier Drogba muscled his way through on goal but Salvatore Aronica and De Sanctis combined to clear the danger as the Ivory Coast international bore ominously close to goal.
Instead, Napoli extended their advantage five minutes later. After Chelsea defender David Luiz gave the ball away sloppily, Cavani turned his marker well and passed across the outside of the area, past an outrushing Cech, for Lavezzi to slot into an empty net.
"We always say we keep working hard on the training ground but unfortunately we don't seem to transport that on the pitch," Cech said. "We have quality players who can turn it around, but it could be better because we don't have time to recover. We have a lot of games coming up and we are not in a position to drop many points in league."
"It's not an ideal situation but we are still in the Champions League and we will fight to the end."
Villas-Boas looked to wrestle back control by summoning Lampard and Michael Essien from the bench, but chances dried up at both ends for a period as Chelsea were visibly affected by conceding the third.
Napoli almost scored again as Cech flapped at a cross but, with the goal gaping, Cavani slipped and Maggio then saw his effort cleared off the line by Ashley Cole.
Chelsea laboured late in search of another away goal, Lampard hitting a testing long shot into De Sanctis' arms in stoppage time, but it ended with Napoli in control of the tie.
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