High-efficiency hybrid solar cells (HSCs) based on electrospun titanium dioxide (TiO2) nanofibers plus poly(3-hexylthiophene) (P3HT) are fabricated by means of both the pretreatment using tetrahydrofuran (THF) vapor and the surface modification using n-type antimony chalcogenide (Sb2S3) on the TiO2 nanofibrous networks. It is revealed that the THF pretreatment not only reinforces the interfacial physical contact but also suppresses the interfacial recombination. The Sb2S3 modification improves the light absorption and charge transfer. Given that the active layer of the HSCs is as thin as 300 nm, it is demonstrated that the power conversion efficiency (PCE) is enhanced over 175%, exhibiting a PCE of 2.32%.