The reigning European champions were soundly beaten by Shakhtar in Ukraine last month and go into this match on the back of a Premier League defeat by Manchester United and a disappointing draw against Swansea on Saturday.
England defender Ashley Cole has been ruled out of Wednesday's game due to a hamstring strain, with Ryan Bertrand expected to replace him at left-back.
Chelsea captain John Terry is though set to return after serving a four-game domestic ban for racially abusing QPR's Anton Ferdinand.
But David Luiz and Juan Mata both face late decisions on whether they can take their place in the starting line-up.
Donetsk are currently leading Group E by three points but di Matteo is confident his side can deal with the pressure and achieve an important victory.
"We need to play the perfect game to beat Shakhtar but we are strong at home and I think we'll be fired up to win it," the former Chelsea and Italy midfielder told a news conference on Wednesday.
"The way they went to Turin (against Juventus) and played there showed what confidence they have.
"But we are a strong team and we will have to put them under pressure and score the goals to win the game.
"I'm confident because this team has a strong wining mentality and the experience of playing in games like his because you don?t feel the pressure so much," di Matteo insisted.
"We certainly have to win our home games and I believe we can do that. With a win it's all in our hands and that's what we want to do."
Chelsea's triumphant run last season saw them reverse a 3-1 deficit at home to Napoli in the last 16 before famously going through to the final after drawing 2-2 against Barcelona at the Camp Nou.
Serbian defender Branislav Ivanovic believes that experience will give them the edge against the Ukranian champions, although he warned the Blues would have to be at their best to stop the attacking threat of Brazilians Wilian, Alex Teixera and Fernandinho.
"All these games are difficult to play because we are under pressure," Ivanovic said. "But we know how we have to approach it if we are going to win the game.
"We will be judged on how we perform defensively and this is where we have to improve. I'm sure we can create chances and score goals so we must work hard on our defensive play. We must be solid and compact in the group stage because the real aim is for us to reach the knockout stage. If we can do that then we can be successful.
Cole suffered his hamstring injury in the 1-1 draw against Swansea at the Liberty Stadium.
Di Matteo admitted it was a major setback to lose a player of his experience but welcomed the return of Terry."
"It's a real blow for us because he has all the experience of playing in big games like this," he said.
"But on the other hand, JT (Terry) is available again so fortunately we will have a lot of experience in our side to be able to win the match."