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Additional photon-harvesting by hole transporting materials in Sb2S3-sensitized solar cell is demonstrated through the formation of electron channels in the hole transporter such as P3HT (poly(3-hexylthiophene)) and 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)) that can act as both a hole conductor and light absorber. As a result, the short-circuit current density is improved with an increment in overall efficiency. These findings provide new insights into use of light-absorbing conjugated polymers as a hole conductor in the inorganic–organic heterojunction sensitized solar cells.