As new-type donor–acceptor π-conjugated dyes capable of forming a strong interaction between the electron-acceptor moiety of the sensitizers and a TiO2 surface, fluorescent dye OH11 and pyridinum dye OH12 with a pyridine and pyridinium ring as the electron-accepting group, respectively, have been designed and synthesized as photosensitizers for use in dye-sensitized solar cells (DSSCs). The fluorescent dye OH11 exhibits an absorption band at around 410 nm and a fluorescence band at around 530 nm. On the other hand, the pyridinum dye OH12 shows an absorption maximum at around 560 nm, assigned to a strong intramolecular charge-transfer excitation from the dibutylamino group to the pyridinium ring. The short-circuit photocurrent densities of the DSSCs prepared by using OH11 and OH12 are 4.33 and 1.74mA cm–2, and the solar energy-to-electricity conversion yields are 1.33 and 0.51 %, respectively, under simulated solar light [AM (air mass) 1.5, 100 mW cm–2]. The open-circuit photovoltage for OH11 (525 mV) is higher than that of OH12 (444 mV). The effects of the configuration of the dyes on the TiO2 surface and of their chemical structures on the photovoltaic performances are discussed on the basis of semi-empirical molecular orbital calculations (AM1 and INDO/S), spectral analyses and cyclic voltammetry.