New hemicyanine dyes (CM101, CM102, CM103, and CM104) in which tetrahydroquinoline derivatives are used as electron donors and N-(carboxymethyl)-pyridinium is used as an electron acceptor and anchoring group were designed and synthesized for dye-sensitized solar cells (DSSCs). Compared with corresponding dyes that have cyanoacetic acid as the acceptor, N-(carboxymethyl)-pyridinium has a stronger electron-withdrawing ability, which causes the absorption maximum of dyes to be redshifted. The photovoltaic performance of the DSSCs based on dyes CM101–CM104 markedly depends on the molecular structures of the dyes in terms of the n-hexyl chains and methoxyl. The device sensitized by dye CM104 achieved the best conversion efficiency of 7.0 % (Jsc=13.4 mA cm−2, Voc=704 mV, FF=74.8 %) under AM 1.5 irradiation (100 mW cm−2). In contrast, the device sensitized by reference dye CMR104 with the same donor but the cyanoacetic acid as the acceptor gave an efficiency of 3.4 % (Jsc=6.2 mA cm−2, Voc=730 mV, FF=74.8 %). Under the same conditions, the cell fabricated with N719 sensitized porous TiO2 exhibited an efficiency of 7.9 % (Jsc=15.4 mA cm−2, Voc=723 mV, FF=72.3 %). The dyes CM101–CM104 show a broader spectral response compared with the reference dyes CMR101–CMR104 and have high IPCE exceeding 90 % from 450 to 580 nm. Considering the reflection of sunlight, the photoelectric conversion efficiency could be almost 100 % during this region.