Metal–organic　frameworks　(MOFs)　materials　featured　large　specific　surface　area,　unique　porous　structure　and　highly　crystalline　nature　which　rendered　them　ideal　catalysts　in　solar　light　conversion.　Generally,　the　catalytic　H2　generation　activity　of　the　MOFs　was　rather　low　which　restricted　its　application.　The　effective　co-catalyst　introduction　could　enhance　its　overall　performance　via　reducing　the　overpotential　of　hydrogen　production　while　facilitating　charges　transfer　and　increasing　reactive　sites.　Herein,　an　two-dimensional　(2D)　O,P–MoS2　nanosheets　cocatalyst　with　adequate　edge-S　active　sites　and　high　1T-phase　content　were　fabricated　via　co-doping　of　O　and　P　atoms.　Rational　coupling　the　2D　O,　P–MoS2　nanosheets　with　2D　NH2-MIL-125(Ti)　nanoplate　can　afford　greatly　improved　photocatalytic　H2　production　rate　of　339.3　μmol⋅g−1⋅h−1,　which　was　11.6　and　6.7　times　of　pure　NH2-MIL-125(Ti)　and　NH2-MIL-125(Ti)/commercial　MoS2　composite,　respectively.　DFT　calculation　revealed　that　the　edge-S　serve　as　the　active　sites　for　H∗　adsorption　rather　than　the　plane-S　and　O　sites　in　O,　P–MoS2　or　the　O　and　S　sites　in　O–MoS2.　Compared　with　the　commercial　MoS2　with　completely　2H-phase,　the　dual-doping　can　create　higher-density　unsaturated　edge-S　atoms　and　more　1T　phase　which　can　improve　the　reactivity　of　NH2-MIL-125(Ti)　via　inducing　the　breaking　of　Mo–S　bonds　and　providing　higher　electrical　conductivity.　Dual　non-metal　atom　doping　of　MoS2　cocatalyst　featured　abundant　edge-S　active　centers　and　high　concentration　of　1T-phase　offered　a　facile　and　effective　method　to　developing　highly　efficient　catalysts　toward　solar-energy　conversion.　©　2023　Hydrogen　Energy　Publications　LLC