Poly(alkoxycarbonylphenylene)s with long alkoxy groups were prepared by dehalogenative polycondensation of alkyl dichlorobenzoates with nickel bromide/zinc/triphenylphosphine catalyst. The poly(alkoxycarbonyl-p-phenylene)s and poly(alkyloxycarbonyl-m-phenylene)s are liquid crystalline, although the latter are composed wholly of kinked repeating units. While poly(hexyloxycarbonylphenylene)s exhibit only thermotropic liquid crystalline behavior, poly(dodecyloxycarbonylphenylene)s and poly(hexadecyloxycarbonylphenylene)s show amphotropism.