Pd　nanoparticles　with　an　average　size　of　1.7　nm　confined　inside　a　MIL-100(Fe)　cavity　(Pd@MIL-100(Fe))　were　prepared　via　double-solvent　impregnation　combined　with　a　photoreduction　process.　Due　to　efficient　coupling　of　photocatalytic　dehydrogenation　and　Pd-based　hydrogenation,　the　resultant　Pd@MIL-100(Fe)　showed　significantly　superior　performance　in　light-induced　N-alkylation　of　amines　with　alcohols　over　Pd/MIL-100(Fe),　in　which　larger　Pd　nanoparticles　(6–12　nm)　deposited　on　the　external　surface　of　MIL-100(Fe)　were　prepared　via　a　conventional　single-solvent　impregnation　followed　by　a　similar　photoreduction　process.　Kinetic　studies　and　controlled　experiments　revealed　that　the　whole　N-alkylation　reaction　is　limited　by　the　photocatalytic　alcohol-to-aldehyde　dehydrogenation　reaction.　This　is　the　first　demonstration　of　light-induced　N-alkylation　of　amines　by　alcohols　over　M/MOFs　nanocomposites　and　also　highlights　the　great　potential　of　using　M/MOFs　nanocomposites　as　multifunctional　catalysts　for　light-induced　organic　syntheses.　©　2016　Elsevier　Inc.