Four novel methacrylate-based side chain donor–π-conjugated–acceptor (D–π–A) type polymers (AT-P1, AT-P2, AT-P3 and AT-P4) were synthesized via free radical polymerization. Variations in the optical, redox and photovoltaic characteristics were introduced by the substitution of different electron-deficient groups and the polymers were employed in the triphenylamine–acridone system. These new push–pull systems are based on acridone (as a π-spacer), several electron-withdrawing anchoring/acceptor groups (malononitrile (MN), nitrobenzene (NB), picolinic acid (PA) and tetrazole (Tz)) and triphenylamine (TPA) as the donor group. A multidisciplinary study concerning the optical, electrochemical and photovoltaic performances of the polymers reveals that the polymer bearing tetrazole acceptor group (AT-P4) exhibited the best overall conversion efficiency (4.20%) as a sensitizer in a dye-sensitized solar cell (DSSC) under AM 1.5 irradiation (100 mW cm⁻²).