Starting from 2,2′-bipyridine dicarboxylic acid, two new (D–π–A)₂ sensitizers, including m-DA with the carboxyl anchoring group substituted meta to the donor-bridge moiety and p-DA with a para-substituted anchoring group, were synthesized in order to evaluate the impact of the position of the anchoring group on the optical, electrochemical, and photovoltaic properties of dye-sensitized solar cells. p-DA exhibits red-shifted absorption behavior compared to m-DA, owing to the more efficiently extended π-conjugation with para substitution. Both m-DA and p-DA are adsorbed on the mesoporous TiO₂ surface by using both of their carboxylic acid groups in a bianchoring mode, which is confirmed through attenuated total reflectance FTIR analysis. Red-shifted absorption of p-DA assists the achievement of a red-shifted incident photon-to-electron conversion efficiency and a higher short-circuit current density than m-DA. The photogenerated electron lifetime in TiO₂ is also found to be higher for para substituted p-DA than the meta-substituted m-DA, which results in a higher open-circuit voltage. All of the results suggest that dicarboxyl-2,2′-bipyridine can be used as an acceptor for metal-free organic sensitizers. However, the anchoring segments should be adjusted to the favorable position of the corresponding donor-bridge moieties for better conjugation.