The 42-year-old has warned his players that they will face an uphill battle in the Champions League this season against sides keen to beat the current holders
In particular, the 42-year-old Blues boss suggested that his squad would have to be vigilant against the likes of Danish side Nordsjaelland, who Chelsea will travel to on Tuesday night, hinting that a loss of concentration could be catastrophic against relative unknowns in this competition.
"We will be a scalp for the teams now. The motivation of the other teams will be stronger because we are the holders," he told The Mirror.
"I am sure a lot of managers will use that to motivate their players."
The Chelsea manager was impressed by the Danes' efforts in their 2-0 defeat to Shakhtar Donetsk: "[Nordsjaelland] had a lot of possession – more than Shakhtar, in fact – and created chances."
Chelsea won the trophy last season despite indifferent domestic form largely due to the side staying focused against strong attacking opposition such as Barcelona and Bayern Munich.
The Stamford Bridge outfit were in danger of going out in the group stages of the competition last year, and Di Matteo is keen to avoid a repeat of the sloppiness that nearly cost them so dearly.
"As for last season, I don't like to look backwards but what we need is to have the concentration for 90 minutes. We conceded a lot of goals late on. We need to stay focused and close the game down."
The Londoners failed to do this in their first group game this year against Juventus, blowing a 2-0 lead to draw at Stamford Bridge against the Italian champions. However, Di Matteo suggested that such is the quality of teams on show, this will be a tough group for his side.
"This was always going to be a tight group with the champions of Denmark, Ukraine and Italy. We need to try to win, for sure."