Sterling has moved to Stamford Bridge from Manchester City this summer, while Koulibaly has arrived from Napoli, and the duo are in line to play their first minutes for the club against Charlotte.
Head coach Thomas Tuchel will make changes to the side that started against Club America last time out, with Edouard Mendy, Reece James, Mason Mount and Jorginho expected to come into the XI.
Koulibaly could feature in a back three alongside Trevoh Chalobah and Thiago Silva, but Sterling's debut for the Blues might come off the bench in the second period.
Tuchel could want to have another look at Conor Gallagher from the first whistle, with the England international potentially featuring alongside Jorginho as part of a midfield two.
Chelsea are missing N'Golo Kante and Ruben Loftus-Cheek on their tour due to their COVID-19 vaccination status, which is likely to open the door for Ross Barkley to earn more minutes.
Callum Hudson-Odoi, who had a frustrating 2021-22 campaign due to injury, could also keep his spot in the final third, with Kai Havertz potentially leading the line.
Marcos Alonso and Cesar Azpilicueta both featured off the bench against America amid the speculation surrounding their futures, and it remains to be seen how involved they are in this contest.
Chelsea possible starting lineup: Mendy; Chalobah, Silva, Koulibaly; James, Jorginho, Gallagher, Chilwell; Hudson-Odoi, Havertz, Mount