The match comes one game into his four-match domestic suspension. Terry will captain the side after Chelsea controversially refused to strip him of the honour over the language he used towards Anton Ferdinand.
Di Matteo said: "He has realised that he used language that was inappropriate and he has apologised for that and has certainly learned from that issue. And with good performances and good behaviour in the future he should still be looked upon as the leader for our club."
The timing could hardly be more ironic, with the defender set to wear an armband bearing the slogan 'Unite Against Racism' as part of a Football Against Racism in Europe (FARE) campaign scheduled for this week.
Terry has never faced a bigger test of character than following the aftermath of his Football Association guilty verdict.
However, Di Matteo said: "I've never been concerned about picking him.
"He's been able to focus on the games and that's what the players love to do, playing football and it's good for them that they can focus on that."
He added: "What is common for players is that, even if they have family problems or some kind of issues outside in their private life, they tend to be able to focus on the football because it kind of just helps them."
Shakhtar will provide Chelsea with a stern test having won their last 21 league matches and 15 of their 16 games this season, taking four points from their first two Champions League outings to lie joint top of Group E. With Juventus just two points behind, it is looking like a three-way battle to reach the knockout stage.
Di Matteo said: "You will probably need more than the 10 points that normally qualifies you."
CHAMPIONS LEAGUE MATCHPACKS - matches 19:45 UK time unless stated
- Sports & Recreation
- Di Matteo