ABSTRACTNovel main-chain liquid-crystal polyurethanes with tertiary amino groups were synthesized. Their thermal properties and orientational behavior were examined. These polyurethanes showed an enantiotropic nematic phase with a schlieren texture. Liquid-crystalline binary systems and a metal-complexed family were obtained from one of these polyurethanes. The liquid-crystalline binary systems, having a polar compound component, formed an induced smectic A phase under heating and cooling. In the induced smectic A phase, a focal conic fan texture and a homeotropic structure were observed. The metal-complexed family also showed an enantiotropic nematic phase.