The synthesis of two copolymers of benzothiadiazole and dihexyldithiophene were obtained by employing oxidative ferric chloride polymerisation and Stille cross coupling polymerisation. Weight average molecular weights of respectively 15200 g mol(-1) and 3200 g mol(-1) were obtained. The polymers have an optical band gap of similar to 2 eV. Photovoltaic devices were prepared using the pure polymer materials and mixtures of the polymers and a soluble fullerene derivative. Efficiencies of 0.024% were obtained. Head-to-head and head-to-tail coupling was not found to influence the maximum photovoltaic performance that could be obtained.