We report the simultaneous dynamic kinetic resolution (DKR) of a secondary alcohol in combination with lipase-catalyzed ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL). (R,S)-1-Phenylethanol (PhE) was used as a model secondary alcohol and incorporated into poly(epsilon-caprolactone) (PCL) under DKR conditions. A total of 75% of the PhE was incorporated as (R)-PhE-PCL with over 99% enantio excess (ee) in 23 h. This methodology could provide a simple one-step approach to prepare enantiopure sustained release polymeric formulations of chiral species such as drugs or drug precursors bearing a secondary hydroxyl group.