AbstractA series of liquid‐crystalline copolymers 1 with a chiral azobenzene moiety as photoreactive mesogenic unit was prepared. The polymers were fractionated and the mesophase behaviour of the high‐ and low‐molecular weight fractions was examined. The copolymers display smectic A and cholesteric phases. For the cholesteric phases the pitch of the helix was determined, which ranges from 3 to 20 μm. Stable monolayers at the air‐water interface were obtained from two monomers and one of the homopolymers. Multilayer assemblies of the azobenzene‐containing polymers can be used to study photo‐induced order/disorder transitions.