A donor backbone [poly(para-divinylphenylamino)]acceptor (cyanoacetic acid side group) type conjugated polymer (P2) has been synthesized and used as the active material for dye-sensitized solar cells. DFT calculation shows that the insertion of vinyl link in the polymer backbone leads to a planar structure in P2 and changes the excited state significantly. Photoelectrochemical cells based on the DSSC format were fabricated using the polymers as sensitizers. The cell constructed using P2 exhibits a considerably high peak IPCE and J-V response, with an overall power conversion efficiency of 3.67%. (C) 2014 Wiley Periodicals, Inc.