We report the synthesis of some new backbone fluorinated polymers of the poly(phenylenevinylene) type. The new polymers were characterised by NMR, SEC and X-ray powder diffraction. The charge carrier mobilities were determined using pulse radiolysis time resolved microwave conductivity (PR-TRMC) and the carrier mobilities were compared to the similar non-fluorinated analogues. The changes in charge carrier mobilities as a function of molecular substitution pattern is discussed in terms of other materials properties such as electronic structure and absorption properties. The major result is that it was found possible for this type of material to alter the electronic energy levels by molecular substitution without imparting significant changes in the magnitude of the charge carrier mobilities and the optical properties.