Two series of dyes have been designed and theoretically characterized through density functional theory and time-dependent density functional theory to systematically explore the structure–property relationship of dyes with D–A–π–A architecture and the performance of dye-sensitized solar cells, particularly the influence of the π-bridge, including its alkyl side chain, adding additional conjugate spacer, displacement, and separation of π-bridge. Key parameters associated with the short-circuit current density Jsc and open-circuit photovoltage Voc were characterized and analyzed in detail. All of the analysis results manifest that dye H1 should be the best candidate to fabricate dye-sensitized solar cells owing to the best optical absorption property (a broad absorption band from 300 to 900 nm for adsorbed dye) and other outstanding parameters.