In this study, we report a facile strategy to prepare a new class of red phosphorus (RP) decorated and doped TiO2 (A: anatase and B: TiO2(B)) nanofibers with boosted photocatalytic hydrogen evolution reaction (HER) performance from pure water. The optimized TiO2(B)/RP and TiO2(A)/RP heterostructure exhibits significantly enhanced photocatalytic performances, with HER rate reaching 11.4 and 5.3 μmol h−1, respectively. The optical absorption of TiO2 is significantly extended to the visible light region after decoration of RP. And more oxygen vacancies (VO) were introduced by phosphorus doping in the TiO2(B)/RP than TiO2(A)/RP. The theoretical calculations illustrate the formation of VO can decrease the ratio of effective masses of electron to hole, which gives rise to promoted photoinduced charge separation and transfer. These results suggest that the boosted photocatalytic HER performance should be mainly attributed to the synergetic enhancement in light harvesting and charge separation enabled by RP deposition and P5+ doping.