Morphological　modulation　of　elemental　red　phosphorus　(RP)　is　achieved　via　a　metallic　nickel　(Ni)-promoted　chemical　vapor　deposition　(CVD)　strategy　to　enhance　its　photocatalytic　hydrogen　generation　activities.　The　presence　of　Ni　in　the　synthesis　facilitates　two　synergetic　effects　on　the　as-prepared　crystalline　RP　photocatalysts:　i)　optimized　architecture　of　regular　microrod　structures　to　increase　the　surface　area　and　reaction　sites;　ii)　Ni　nanoparticle　on　the　RP　serves　as　the　co-catalyst　to　suppress　the　undesired　deep　charge　trapping　and　recombination　by　improving　the　surface　charge　separation　efficiency.　As　a　result,　the　optimized　Ni@RP　catalyst　demonstrates　a　ca.　12-fold　enhancement　in　the　visible-light　photocatalytic　hydrogen　evolution　than　that　of　the　amorphous　RP.　The　discovery　of　the　natural　growth　of　elemental　P　promoted　by　transition　metal　catalysts　in　this　work　may　provide　new　insights　into　developing　other　favorable　elemental　catalysts　for　various　applications.　©　2022