Sb2S3-sensitized mesoporous-TiO2 solar cells using several conjugated polymers as hole-transporting materials (HTMs) are fabricated. We found that the cell performance was strongly cc rrelated with the chemical interaction at the interface of Sb2S3 as sensitizer and the HTMs through the thiophene moieties, which led to a higher fill factor (FF), open-circuit voltage (V-oc), and short-circuit current density (J(sc)). With the application of PCPDTBT (poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) as a HTM in a Sb2S3-sensitized solar cell, overall power conversion efficiencies of 6.18, 6.57, and 6.53% at 100, 50, and 10% solar irradiation, respectively, were achieved with a metal mask.