The　attainment　of　rapid　charge　mobility　and　effective　N2　activation　is　of　critical　importance　for　photocatalytic　nitrogen　fixation　but　it　has　always　been　a　challenge.　Such　challenge　may　be　met　by　the　construction　of　a　Type　II　MoS2　nanoparticles/　MIL-100(Fe)　heterojunction　photocatalyst.　The　new　material　possesses　charge　migration　channels　that　facilitate　the　separation　of　photogenerated　carriers.　This　charge　redistribution　during　photocatalysis　is　confirmed　by　experimental　results　showing　a　decrease　of　charge　density　on　the　Fe　species　and　an　increase　of　that　on　Mo.　Moreover,　DFT　calculations　show　that　the　adsorption　of　N2　and　H2O　is　more　likely　to　occur　on　Fe　sites　and　Mo　sites,　respectively.　These　findings　clearly　suggest　a　drastically　improved　spatial　isolation　of　reduction　and　oxidation　sites　on　the　photocatalyst　as　compared　to　pristine　MIL-100(Fe).　The　optimized　MoS2/MIL-100(Fe)　exhibits　a　NH4+　yield　rate　of　1.29　μmol·h−1　as　excellent　utilization　of　photoinduced　electron-hole　pairs　and　effective　adsorption　and　activation　of　N2　become　possible.　This　work　offers　an　insight　on　the　synergy　of　heterojunction　engineering　with　coordinated　activation　for　photocatalytic　ammonia　synthesis.　©　2025　Elsevier　Inc.