A　Pt@MIL-101(Fe)　nanocomposite,　with　Pt　nanoparticles　(NPs)　fully　embedded　and　well　dispersed　in　the　matrix　of　MIL-101(Fe),　was　prepared　via　a　microwave-assisted　self-assembly　of　MIL-101(Fe)　in　the　presence　of　PVP-capped　Pt　colloids　(PVP　=　polyvinylpyrrolidone).　The　as-obtained　Pt@MIL-101(Fe)　nanocomposite　shows　a　superior　activity　for　the　one-pot　reaction　between　o-phenylenediamines　and　alcohols　to　synthesize　benzimidazoles　under　visible　light,　with　concomitant　generation　of　clean　energy　hydrogen,　ascribed　to　an　efficient　mass　diffusion　and　substrate-catalyst　interactions　imparted　by　the　MOFs.　The　embedding　of　the　Pt　NPs　within　the　MIL-101(Fe)　contributes　to　the　relatively　high　stability　of　Pt@MIL-101(Fe),　since　the　aggregation　of　the　Pt　NPs　can　be　significantly　inhibited.　This　study　not　only　provides　a　green　and　atom-efficiency　strategy　for　the　synthesis　of　benzimidazoles　with　concomitant　generation　of　clean　hydrogen,　but　also　demonstrates　that　a　rational　fabrication　of　metal　NPs/MOFs　nanocomposites　is　important　for　them　to　be　used　as　multifunctional　catalysts　for　light　initiated　one-pot　tandem/cascade　reactions.　©　2022　Elsevier　Inc.