A diversity of poly(bis-3,4-ethylenedioxythiophene methane)s have been carefully designed and synthesized by chemical oxidation polymerization and then been employed as novel counter electrodes in dye-sensitized solar cell (DSC). The relationship between monomer structures and their effects on DSC are thoroughly investigated. After optimization, their photo-electron conversion efficiencies of 5-7% are obtained, which are a little bit lower than that of traditional sputtered Pt counter electrode. Our results indicate that poly(bis-3,4-ethylenedioxythiophene methane) is a new kind of promising conductive polymer and may be able to compete with the wellknown poly(3,4-ethylenedioxythiophene) (PEDOT). In addition, the monomers' substitution groups have a big influence on corresponding polymers electrodes DSC performance, which reveals that there is much room for improvement. Moreover, great prospects of other organo-electronic application would be expected for such type of polymers.