Endowing　photocatalyst　with　functional　nanostructure　can　effectively　improve　its　performance　towards　solar　energy　conversion.　Here,　a　unique　Ni–Fe-based　mesoporous　hollow　spherical　nanostructure　(NiFeOx/NC-t)　was　facilely　constructed　via　the　direct　thermal　decomposition　of　Ni-BTC@PBA　composites.　The　hybrids　consist　of　in-situ　formed　nitrogen-enriched　carbon　layers　constituting　the　mesoporous　walls　of　hollow　spherical,　and　amorphous　NiFeOx　nanoparticles　and　a　small　fraction　of　FeNi3　are　embedded　on　the　spherical　walls　during　carbonization.　After　loading　EY　molecules　on　NiFeOx/NC-t　as　solar　light　absorbers,　an　optimal　photocatalytic　hydrogen　evolution　rate　of　5352.7　μmol　g−1　h−1　was　achieved　with　excellent　stability　under　visible　light　(λ　＞　420　nm)　in　the　absence　of　co-catalyst.　The　excellent　photocatalytic　activity　was　revealed　to　be　ascribed　to:　)　mesoporous　hollow　spherical　structure　having　a　large　surface　area,　thus　exposing　more　active　sites;　)　efficient　injection　of　photo-generated　electrons　from　excited　EY−　into　NiFeOx　and　FeNi3　by　the　bridge　of　high-conductive　nitrogen-enriched　carbon　layer.　In　brief,　the　structural　and　compositional　features　synergistically　strengthen　the　photocatalytic　activity　of　NiFeOx/NC-t.　It　is　worth　noting　that　MOF-derived　route　can　significantly　simplify　the　preparation　process　of　mesoporous　hollow　spherical　nanostructure.　This　work　provides　an　approach　for　facile　preparation　of　versatile　photocatalysts　with　high　efficiency　for　solar　energy　conversion.　©　2022　Hydrogen　Energy　Publications　LLC