Liquid crystalline copoly(vinyl ether)s based on i-butyl vinyl ether and 11-[(4’-cyano-4-biphenyl)oxy]undecanyl vinyl ether of various compositions were synthesized. The copolymers exhibited smectic A mesomorphism with a layer thickness strongly increasing with increasing i-butyl vinyl ether content. The intermesogenic distance remained unchanged. A model of the layer structures is given based on structural assessments from small-angle X-ray scattering data.