PdAu@MIL-100(Fe),　with　PdAu　alloy　nanoparticles　of　ca.　1.7　nm　encapsulated　inside　MIL-100(Fe)　cavities,　were　prepared　via　a　double-solvent　impregnation　followed　by　photoreduction.　As　compared　with　bare　Pd@MIL-100(Fe),　bimetallic　PdAu@MIL-100(Fe)　showed　superior　activities　for　the　tandem　reactions　between　amines　and　alcohols　to　produce　N-alkyl　amines　under　visible-light　irradiation,　ascribed　to　the　promoting　effect　of　metallic　Au　in　the　photocatalytic　alcohol-to-aldehyde　dehydrogenation.　A　Pd/Au　ratio　dependent　N-alkylation　activity　was　observed　over　PdAu@MIL-100(Fe),　implying　the　possibility　of　synchronizing　the　reaction　rates　of　two　consecutive　steps　in　the　N-alkylation　reaction,　i.e.,　photocatalytic　alcohol-to-aldehyde　dehydrogenation　and　imines　hydrogenation,　to　optimize　the　whole　reaction.　This　study　provides　a　highly　efficient　and　stable　catalytic　system　for　the　realization　of　alkylation　of　amines　via　a　successful　coupling　of　MOF-based　photocatalysis　and　metal　nanoparticle-based　hydrogenation.　This　work　also　demonstrates　that　the　reaction　rates　of　different　catalytic　steps　in　a　cascade/tandem　reaction　can　be　synchronized　for　an　efficient　overall　reaction　via　a　rational　design　of　the　multifunctional　catalysts.　©　2018　Elsevier　Inc.