A general and inexpensive procedure for the synthesis of poly(arylene)-type homopolymers and copolymers containing alternating oligophenylene and a functional group (X) (e.g. X = -O-, -CO-, -SO2-, -C(CH3)(2)-, -CH2-CH(Et)-, etc) is described. The synthetic method is based on the Ni(0)-catalyzed homocoupling of aryl bismesylates (MsOAr-X-ArOMs) derived from bisphenols. Symmetric X groups lead to regioregular crystalline and insoluble polymers whereas bulky, asymmetric X groups or the incorporation of comonomers yield regioirregular polymers and, respectively, copolymers with decreased crystallinity and increased solubility. This new synthetic method can be applied to the preparation of polymers with controlled rigidity which are amorphous, crystalline or liquid crystalline.