The synthesis of a series of poly(arylene vinylene)s via transition metals catalysed polycondensation with a view to producing well defined and clean samples for study , particularly for the incorporation of the material in light emitting devices has been described. Initially the McMurry reaction was applied in the synthesis of poly(4,4'-diphenylene diphenylvinylene). The reaction conditions have been optimised and relatively high molecular weight polymers with narrow molecular weight distributions were produced by fractionating the polymer. The feasibility of the McMurry reaction was established in the synthesis of related polymers; including poly(l,3-phenylene diphenylvinylene), poly(l,3-phenylene dimesitoylvinylene) and poly(4,4'-diphenylene-l,2-bis(pentafluorophenyl)vinylene). In other attempts the Yamamoto and Suzuki polycondensations were applied in the synthesis of structurally defined poly(arylene vinylene)s which could not be made via the route used earlier. Studies on UV-visible absorption, photoluminescence and electroluminescence properties of polymers produced were carried out and correlation between polymer structure and electro-optical properties of the polymer, particularly photoluminescence has been established.