Four new donor–acceptor type polymeric metal complexes (P1, P2, P3, and P4) with the same Cd(II) complex in side chain and different conjugated backbone structures were synthesized by Yamamoto coupling and applied in dye-sensitized solar cells (DSSCs) as photosensitizers. The photophysical, electrochemical, and thermal properties were investigated in detail, showing that conjugated backbone containing fluorene improved intramolecular charge transfer and increased generation of photocurrent. The highest power conversion efficiency of 0.56% (J sc = 1.63 mA cm−2, V oc = 0.69 V, FF = 0.50) was obtained with a DSSC based on P3 under simulated air mass 1.5 G solar irradiation, which shows a new strategy to design photosensitizers for DSSCs. [ABSTRACT FROM AUTHOR]