Chelsea reached the semi-finals of the Champions League for a sixth time after a thrilling second leg comeback to knock out Napoli, playing with more freedom and confidence since Italian Di Matteo replaced the sacked Villas-Boas in early March.
Holders Barcelona represent formidable opponents but the likes of Didier Drogba, Frank Lampard and John Terry will walk out at Stamford Bridge for the first leg with no trepidation and fuelled with a desire to avenge a bitter semi-final defeat in 2009.
The sides have met four times in the knockout phase of the tournament with Barca prevailing three times, most notably three years ago when Chelsea were on the brink of reaching the final before Andres Iniesta's stunning stoppage time strike broke their hearts and sent Drogba apoplectic with rage.
Drogba warmed up for another meeting with Barca with a spectacular goal in the 5-1 FA Cup semi-final victory over Tottenham Hotspur on Sunday, while Lampard scored a sensational free kick and Terry produced some defensive heroics.
All three have been instrumental in the club's upturn in fortune since Villas-Boas left.
Di Matteo is holding the fort while owner Roman Abromovich decides on a new general, with Barca's Pep Guardiola one of the names mentioned, but the Italian appears to have unified a fractured dressing room - crucially getting the best out of the club's old warriors.
"Robbie has been brilliant, he took over a team that was looking like going out of the Champions League, struggling in the league," Lampard told Chelsea's website.
"He loves the club, he has brought confidence into the dressing room, spoke to all the players and you can see the response he has got."
Barca have been on a dizzying run of form, winning 14 of their last 15 matches and drawing the other 0-0 against AC Milan in the Champions League quarter-final first leg.
Lionel Messi has scored 26 goals in 14 games during that run and the Argentine World Player of the Year has set a new Champions League season record of 14 goals.
His incredible 63 goals in all competitions this term is only four short of the all-time season record of 67 set by former Bayern Munich striker Gerd Muller in 1972/73.
"All that matters in the two games is that we perform on the night. Barcelona have so many players that can hurt you, the greatest player in the world in Lionel Messi so it's a tough task for us but we have to be confident," Lampard said.
If Chelsea can shackle Messi they have half a chance of knocking out the holders as they did in 2005.
"Messi is decisive, and when you have the best player in the world in your team, you tend to become a little dependent on him because he is goal-hungry and in any match he can be the decisive element," said Barca midfielder Javier Mascherano.
The first leg comes three days before crucial domestic league fixtures for both clubs.
Barcelona have cut Real Madrid's lead at the top of La Liga back from 10 points to four over the last month and host Jose Mourinho's side, who play Bayern Mun
