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.
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."
"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.
"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.
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
