Block copolymers of liquid crystalline 6-(4-cyanobiphenyl-4'-oxy) hexyl acrylate (LC6) and cyclohexene oxide (CHO) were obtained by the combination of atom transfer radical polymerization (ATRP) and promoted cationic polymerization (PCP). In the first part, a bifunctional initiator containing benzoin and halide groups in the same structure was used as an initiator in ATRP of LC6, in diphenyl ether in conjunction with CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine as a catalyst. The obtained photoactive liquid crystalline polymers poly[6-(4-cyanobiphenyl-4'-oxy)hexyl acrylate] (PLC6), were used to induce polymerization of CHO through formation of electron donor polymeric radicals upon photolysis and subsequent oxidation to corresponding carbocations in the presence of onium salt. The spectral, thermal and optical measurements confirmed a full combination of ATRP and PCP, which resulted in the formation of AB-type block copolymers. (C) 2007 Wiley Periodicals, Inc.