One of the effective strategies to enhance the photovoltaic performance of polymer solar cells (PSCs) is to synthesize random copolymers composed of one electron donating unit and two different electron accepting units, if the absorptions of two electron accepting units are complementary to each other. To this end, we synthesized a new series of conjugated random copolymer composed of bithiophene (electron donating unit) with thiophene-capped diketopyrrolopyrrole (TDPP) and pyridine-capped diketopyrrolopyrrole (PyDPP) (co-electron accepting units). The random copolymers show broad light absorption and face-on orientation on the substrate, which is beneficial to achieving high short circuit current. The open circuit voltage of the random copolymer can also be controlled systematically by varying the ratio of PyDPP to TDPP in the copolymer, since the HOMO energy level becomes deeper as the PyDPP content in the random copolymer is increased. Consequently, the solar cell device made of the random copolymer with the ratio of 3:1 (TDPP:PyDPP) shows higher PCE (8.11%) than those made of corresponding homopolymers, PTDPP2T (6.70%) and PPyDPP2T (4.14%).