The　urgent　need　to　develop　a　sustainable　and　environmentally　friendly　method　for　synthesizing　organophosphine　compounds　is　underscored　by　their　extensive　applications　in　organic　synthesis,　coordination　chemistry,　medicinal　chemistry,　and　photoelectric　materials.　Metalated　covalent　organic　frameworks　(MCOFs),　which　seamlessly　integrate　the　inherent　photo　properties　of　COF　with　the　catalytic　capabilities　of　metal　ions,　offer　an　optimal　material　for　efficient　transformation　of　organics　sustainably.　In　this　study,　we　introduce　a　simple　COF　with　nickel　anchorages　(Bpy-COF-NiCl2)　as　a　unimolecular　metallaphotocatalytic　system　for　effective　C-P　bond　formation.　This　heterogeneous　photocatalyst　exhibits　superior　catalytic　performance,　achieving　yields　of　up　to　95　%,　and　demonstrates　broad　substrate　tolerance　and　functional　group　reactivity.　Notably,　the　metallaphotocatalytic　system　has　demonstrated　the　capability　to　process　aryl　bromides　to　produce　the　desired　product,　a　feat　not　previously　reported.　Finally,　the　production　and　reusability　test　at　the　gram　scale　attests　to　its　superior　practicality　for　designing　future　organic　cross-coupling　reactions.　Nickel-anchored　COF　(Bpy-COF-NiCl2)　represents　a　unimolecular　heterogeneous　metallaphotocatalysis　system,　adept　at　efficient　C-P　bond　construction.　The　synthesized　photocatalyst　demonstrates　superior　catalytic　performance,　achieving　up　to　a　95　%　yield.　Furthermore,　it　exhibits　a　broad　substrate　scope　and　tolerance　for　various　functional　groups.　Notably,　this　metallaphotocatalytic　system　has　been　found　to　process　aryl　bromides　seamlessly,　yielding　products　previously　unreported　in　similar　systems.image