A　rational　design　of　MNPs@MOFs　(MNPs　=　metal　nanoparticles,　MOFs　=　metal-organic　frameworks)　nanocomposites　is　important　for　their　application　as　multifunctional　catalysts　for　light-initiated　one-pot　tandem/cascade　reactions.　Herein,　the　Pd@MIL-100(Fe)　nanocomposite　with　a　core-shell　structure,　in　which　Pd　colloids　of　ca.　3　nm　are　encapsulated　inside　the　matrix　of　MIL-100(Fe),　was　constructed　successfully　via　self-assembly　of　MIL-100(Fe)　in　preformed　PVP-capped　Pd　colloids　(PVP　=　polyvinylpyrrolidone)　at　room　temperature.　Via　a　successful　combination　of　MOF-based　photocatalysis　with　Pd-based　hydrogenation,　Pdrpvp@MIL-100(Fe),　with　PVP　partially　removed,　exhibited　superior　performance　for　the　reaction　between　nitro　aromatics　and　benzyl　alcohols　to　produce　secondary　amines.　Comparison　of　activity　over　Pdrpvp@MIL-100(Fe)　with　that　of　the　other　two　types　of　MNPs/MIL-100(Fe)　nanocomposites　suggests　that　its　superior　activity　can　be　attributed　to　the　presence　of　well-stabilized　stable　Pd　nanoparticles　(NPs)　for　hydrogenation　and　the　unoccupied　cavities　in　MOFs　to　promote　the　mass　diffusion,　especially　in　the　case　of　larger　substrates,　as　well　as　an　efficient　charge　transfer　from　the　MOF　to　Pd　NPs　for　their　cooperation.　This　study　indicates　that　a　rational　strategy　in　the　construction　of　metal　NPs/MOFs　nanocomposites　is　important　for　their　application　as　multifunctional　catalysts　for　light-initiated　one-pot　tandem/cascade　reactions.　©　2025　American　Chemical　Society.