Ballack is set to play at Stamford Bridge for the first time since leaving the Blues just over a year ago when Bayer Leverkusen begin their Group E campaign against the Blues.
The 34-year-old has the unique honour of being the only man to play in the biggest game in both clubs' history, inspiring Leverkusen to the 2002 Champions League final before starting for Chelsea in the 2008 showpiece.
Unfortunately, the midfielder ended up on the losing side on both occasions, but it was perhaps the penalty shootout heartache in Moscow that was the more difficult defeat to take, with Ballack saying: "It will haunt all of us for ever."
Former Germany captain Ballack, who turns 35 this month, will receive a special presentation from Chelsea in recognition of his four years' service before kick-off on Tuesday night.
He said: "The presentation is a very nice gesture and it will be a very emotional moment for me tomorrow [Tuesday].
"There are still a few players there and some who left in the meantime who I am still friends with and whom I am still in touch with, and also a few of the staff.
"When I moved to Chelsea, it was a big, big challenge and experience for me at the time to play with so many good players.
"If I look back, I had a very good time. I feel always welcomed by the fans and the club. They treat me always very well and we had success.
"We missed a few chances, but we had some successes and I will remember this always and it is a big part of my career."
Bundesliga runners-up Leverkusen will be underdogs but Ballack said: "It is just a game of football, although we are aware there are some big names on the other side.
"We will have our chances."
Chelsea boss Andre Villas-Boas may not field his first-choice XI with Sunday's Barclays Premier League trip to Old Trafford on the horizon.
"You'll see some changes tomorrow [Tuesday]. Then we'll make wise decisions for Sunday," said Villas-Boas, whose big decision once again revolves around whether or not to select Fernando Torres.
Daniel Sturridge certainly did enough to start alongside or instead of the misfiring Spaniard in Saturday's Barclays Premier League win at Sunderland, although Villas-Boas was reluctant to lavish praise on the 22-year-old.
He said: "He had a three-game ban and has just returned, and he had motivation to have an impact in that game. It was the team, also, who made him perform to that level."
Didier Drogba will miss the game as he continues his recovery from his sickening head injury.