The New Zealand outside back replaces Jono Gibbes after the veteran lock was ruled out for six weeks with a hamstring injury.
Chiefs coach Ian Foster said: "Mils is a quality, experienced footballer and has a good feel of where the team is at. The extra responsibility that comes with being captain is a new challenge for him in his rugby career."
Foster has also recalled scrum-half Brendon Leonard after a thigh injury suffered in the defeat to the Waratahs.
Muliaina will lead the team from full-back, with Dwayne Sweeney and Callum Bruce returning to midfield.
Tom Harding (openside) and Faifili Levave (blindside) get their first starts as flankers, with Kristian Ormsby ruled out for the season with a shoulder injury.
Chiefs: M Muliaina, S Anesi, D Sweeney, C Bruce, S Sivivatu, S Donald, B Leonard; S Davison, T Willis, B May, T Lynn, K O'Neill, F Levave, T Harding,Â S Lauaki.
Reserves: V Kamo, B Castle, H Hopgood, L Messam, T Latimer, D Bason, L Masaga.