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Before long, however, Napoli got into gear and drew first blood on the quarter-hour mark when a quick break allowed Dries Mertens to flash a diagonal ball into the box, where Gonzalo Higuain chested down and powered home.
The Partenopei then doubled their lead in the 23rd minute courtesy of a masterful goal which saw Higuain power down the channel before curling a low ball for Marek Hamsik who, without breaking stride, lashed into the bottom right corner from the edge of the area.
For a while following their goal, Napoli took complete control of the game, but Wolfsburg ended the half strongly as Andre Schurrle forced a fine fingertip save from Mariano Andujar on the stroke of half time.
As with the first half, Dieter Hecking's charges began the second period brightly, but were soon under the cosh once again as Diego Benaglio kept out a seemingly goalbound effort by the unmarked Higuain.
There was cause for concern when Miguel Britos nearly sliced a Wolfsburg effort into his own net, but Napoli regrouped and struck a third just after the hour through Hamsik, who was given free rein inside the hosts' box following some farcical defending.
The visitors, however, were home and dry by this point and were able to see the rest of the game out to take an emphatic lead into the second leg at the San Paolo next week.