The importance of maintaining the pressure on Premier League leaders Manchester United will inevitably provide a more powerful incentive to the Blues, but Di Matteo's side are also anxious to end a run of four straight league defeats against the Anfield club
Chelsea savoured success by beating Liverpool in last season's FA Cup final, but with the current title race threatening to be a tight, three-way battle between the Blues, United and Manchester City, league points are now the immediate priority.
Manager Di Matteo said: "They are our bogey team. They seem always to play exceptionally well against us and get results. It is always difficult and very difficult to beat them.
"It hasn't happened too often in the last three years. We have to be aware of that and be very focused and try to play a very good game.
"First of all, they have very good players and they seem to have an exceptional game, one of their best of the season, whenever they play us.
"They always find to play us in a moment when we are not at our best. Sunday, we are in good spirits, full of confidence and the team is playing well. Hopefully it will be a different story."
Di Matteo's desire to reverse the recent trend will be shared by Fernando Torres who has yet to score against his former club since his £50 million move in January 2011.
Torres' performances have improved this season and he scored in the midweek Champions League victory over Shakhtar Donetsk but the Spain international has yet to reproduce the form he showed at Anfield.
"Sometimes playing against your old team gives extra motivation, sometimes it inhibits you," said Di Matteo. "It depends on his frame of mind playing against his old team.
"I am happy with his contribution. It is not about him repaying my faith. It's about him performing for the club. I hope every player feels they have the confidence of the manager."
Martin Skrtel, the Liverpool defender, shares Di Matteo's view that Torres - who has scored seven goals this season - remains a potent force.
Skrtel said: "Even if he isn't scoring goals at the moment he is still one of the best strikers in the world and still dangerous.
"I haven't seen Chelsea play too many times this season but from what I've heard his performances are better than last season."
Torres is certain to start but John Terry's inclusion on his return from a four-match domestic ban is far from guaranteed after Di Matteo's decision to leave the Chelsea captain on the bench against Shakhtar.
Liverpool manager Rodgers is more concerned with the threat offered by Juan Mata, Eden Hazard and Oscar who have provided Chelsea with a different attacking dimension this season.
Rodgers' side have only managed two Premier League wins in their 10 matches so far this season and the Reds already trail Sunday's opponents by 13 points.
But the manager, who rested nine players for the 1-0 defeat to Anzhi in the Europa Leauge, maintains there is nothing to fear in the trip to London.
He said "Chelsea are very dynamic, they're great technicians. They have three No 10s in their team really.
"They have Oscar, (Eden) Hazard and (Juan) Mata and we know the danger that they possess between them.
"You can't do everything to stop world-class players. They will always find space, find ways around what you do. So my focus will be on how we play."
"Stamford Bridge is always a difficult place to go and get a result but we will go there with confidence. We've got some top players who can hurt anybody on a given day."
Reds defender Glen Johnson is set to face his former club but Rodgers will make a late decision on goalkeeper Pepe Reina, who has been struggling with a groin injury.