In this article, we present the results of a study of the preparation of a cyclohexene oxide (CHO) mid‐chain functional macromonomer via ATRP of styrene (St) and epoxidation on work‐up with 3‐chloroperoxybenzoic acid. The ATRP initiator, Br? CH? Br, was synthesized by the condensation of 3‐cyclohexene‐1,1‐dimethanol with 2‐bromopropanoyl bromide. The ATRP of St with Br? CH? Br and Cu(I)/bpy yielded well‐defined polystyrene with a cyclohexene mid‐chain group (PSt? CH? PSt). Epoxidation of the PSt? CH? PSt was performed using 3‐chloroperoxybenzoic acid. GPC, IR and 1H NMR analyses revealed that a low polydispersity macromonomer of polystyrene with CHO functionality at the mid‐chain (PSt? CHO? PSt) was obtained. The photoinduced cationic polymerization of PSt? CHO? PSt yielded comb‐shaped and graft copolymers.