In　this　work,　we　constructed　a　red　phosphorus　(RP)/TiO2　composite　system　via　a　chemical　vapor　deposition　strategy.　The　evolution　of　the　fibrous　phased　RP　nanorods　on　the　surface　of　anatase　TiO2　spheres　was　rationally　adjusted　by　controlling　the　composition　of　precursors.　The　optimal　RP/TiO2　composite　exhibited　a　significantly　enhanced　visible-light-driven　photocatalytic　H2　generation　rate　of　681　mu　mol　h-1　g-1.　The　tightly　interior　surface　bonding　between　RP　and　TiO2　greatly　promoted　the　efficient　charge　transfer　and　redistribution　by　suppressing　the　charge　recombination　and　self-trapping　processes　within　TiO2,　resulting　in　prolonged　lifetimes　of　the　active　charges　during　the　photocatalytic　process　as　investigated　in　detailed　using　femtosecond　time-resolved　transient　absorption　(fs-TA)　spectroscopy.