The former Liverpool midfielder was one of three players handed their first starts of the season by coach Carlo Ancelotti who unusually named his side 24 hours early.
Yury Zhirkov will play alongside skipper John Terry in central defence while Daniel Sturridge will join Nicolas Anelka and Florent Malouda in an attacking line-up.
Frank Lampard and Ashley Cole have not travelled
"We score a lot of goals, we started well this season but you have to pay attention to every game," Ancelotti told Chelsea's website on Tuesday.
Chelsea have scored 17 goals in four Premier League games this season and will be expected to add to their tally against Zilina who are making their debut in the group stages.
However, Ancelotti warned against complacency.
"We are here to win obviously because we want to start this season well. Our aim is to win this group but it will not be easy," the Italian said.
"Every team has a quality and tomorrow Zilina can show fantastic motivation because for them it is an important game against Chelsea and we have to pay attention to this."
Team: 1-Petr Cech; 2-Branislav Ivanovic 26-John Terry, 18-Yury Zhirkov, 33-Alex; 10-Yossi Benayoun, 12-John Obi Mikel, 5-Michael Essien, 15-Florent Malouda; 23-Daniel Sturridge; 39-Nicolas Anelka.
‘He instantly popped into our ratings as one of the best U21 midfielders in Europe. The impressive thing is Slot has made him into more of a no.6' Inside Ryan Gravenberch's transformation at Liverpool
‘I don’t think Liverpool would look at Ollie Watkins, a striker isn’t a pressing issue for them – it’s Arsenal who need one’ Former Reds star explains why his old club don’t need an out-and-out forward this summer
