p-(2,2′-Diphenylethyl)styrene (DPES) was polymerized with the homochiral postmetallocene catalyst dichloro{trans-1,2-dithiocyclohexanediyl-2,2′-bis(4,6-di-tert-butylphenolato)}titanium/MAO. Optically active isotactic polymers were obtained by a controlled reduction of the molecular weight, employing diethylzinc as CTA. Polymers with molecular weights below Mn of 50,000 g mol−1 showed specific rotation values ([α]23D) between ±0.2 and 2.2.