The synthesis, characterization, optical and electrochemical properties of a regioregular copolymer, poly(3-octylthiophene-2,5-diyl-co-3-decyloxythiophene-2,5-diyl) (POT-co-DOT), and an alternating regioregular copolymer poly{(9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-decyloxythien-2-yl)-2,1,3-benzothiadiazole]-5′,5″-diyl} (PF-co-DTB) is disclosed. The incorporation of 3-alkoxythiophene units onto the conjugated backbones enhances the electron-donating property of the polymer and lowers its bandgap. The fabrication and performance of photovoltaic cells with bulk heterojunction architecture based on blends of these copolymers with PCBM are also described.