The Milram superstar, who has won 40 stages in Grand Tours, was beaten into second by Lampre's Bennati on day one but made no mistake this time around, defeating Reynes of Caisse D'Epargne by half a bike's length.
Raul Alarcon (Saunier Duval), Jose Ruiz (Andalucia), Seragin Martinez (Karpin) launched a breakaway moments into the 148km stage which began and finished in Calp and were swiftly joined by Luca Solari (LPR).
They built up a maximum lead of 4:05 following the category one climb of the Montana De La Etapa but were caught after 128km, just before the second third cat climb of the day.
Petacchi gains revenge
That set up the inevitable bunch finish which the Italian claimed to take the overall lead by two seconds from his compatriot Bennati.
Pro Tour 2007
Petacchi seals victory
Wins for Petacchi, Karpets