Abstract A novel graft copolymer consisting of poly(n-octylallene-co-styrene) (PALST) as backbone and poly(ɛ-caprolactone) (PCL) as side chains was synthesized with the combination of coordination copolymerization of n-octylallene and styrene and the ring-opening polymerization (ROP) of ɛ-caprolactone. Poly(n-octylallene-co-styrene) (PALST) backbone was prepared from the copolymerization of n-octylallene and styrene with high yield by using the coordination catalyst system composed of bis[N,N-(3,5-di-tert-butylsalicylidene)anilinato]titanium(IV) dichloride (Ti(Salen)2Cl2) and tri-isobutyl aluminum(Al(i-Bu)3). The molar ratio of each segment in the copolymer, and the molecular weight of the copolymer as well as the microstructure of the copolymer could be adjusted by varying the feeding ratio of both styrene and n-octylallene. The hydroxyl functionalized copolymer PALST–OH was prepared by the reaction of mercaptoethanol with the pendant double bond of PALST in the presence of radical initiator azobisisbutyronitrile (AIBN). The target graft copolymer [poly(n-octylallene-co-styrene)-g-polycaprolactone] (PALST-g-PCL) was synthesized through a grafting-from strategy via the ring-opening polymerization using PALST–OH as macroinitiator and Sn(Oct)2 as catalyst. Structures of resulting copolymer were characterized by means of gel permeation chromatography (GPC) with multi-angle laser light scattering (MALLS), 13C NMR, 1H NMR, DSC, polarized optical microscope (POM) and contact angle measurements.