Novel H3PW12O40-MIL-101(Cr)/TiO2nanofibrous catalysts with outstanding deep-desulfurization performance were successfully obtained via electrospinning combined with a one-pot hydrothermal method in this study. The crystal phase of TiO2as well as the morphology and composition structure of H3PW12O40-MIL-101(Cr)/TiO2nanofibrous catalysts were characterized, and the desulfurization performance of H3PW12O40-MIL-101(Cr)/TiO2nanofibrous catalysts was extensively studied. At an O/S molar ratio of 4:1, 99% desulfurization efficiency could be achieved at 50 °C using 0.02 g of n[H3PW12-MIL-101(Cr)]/m(TiO2) (n/m= 1:5.78) nanofibers as catalysts within 180 min. Further, the recyclability of catalysts and potential mechanism of the desulfurization reaction were analyzed in detail.