Fully　utilizing　the　photogenerated　electrons　and　holes　in　a　photocatalytic　process　is　a　promising　way　to　enhance　catalytic　efficiency　and　achieve　atomic　economy.　Here,　conjugated　photocatalytic　redox　reactions,　i.e.　hydrogenation　of　cinnamaldehyde　(CAL)　to　cinnamyl　alcohol　(COL)　and　concomitant　oxidation　of　benzylalcohol　(BA)　to　benzaldehyde　under　visible　light,　are　achieved　via　creating　bimetal　MIL-100(Fe1-xAlx)　compounds　as　photocatalysts.　MIL-100(Fe0.63Al0.37)　exhibits　a　high　conversion　(≈100%)　of　CAL　with　a　high　selectivity　(≈100%)　of　COL,　while　converts　BA　into　benzaldehyde　(BAD)　with　a　high　yield　(≈100%).　MIL-100(Fe0.63Al0.37)　offers　abundant　and　strong　surface　Lewis　acid　sites　(Al3+)　to　activate　CAL　and　BA　molecules.　In　situ　FTIR-DRS　result　indicates　that　COL　is　selectively　activated　via　a　sbndC[dbnd]O　coordination.　In　situ　EPR　result　reveals　that　BA　molecule　is　activated　to　generate　Ph-CH2O¯　and　H+.　Under　visible　light,　Ph-CH2O¯　is　oxidized　to　Ph-CH2O·　by　photogenerated　hole,　while　the　photogenerated　electron　is　responsible　for　producing　H　atom　through　the　reduction　of　the　dissociated　H+.　Then　the　second　H　atom　is　released　from　Ph-CH2O·,　causing　the　generation　of　Ph-CHO.　The　activated　CAL　is　selectively　hydrogenated　to　COL　by　two　H　atoms.　This　work　provides　a　special　horizon　to　effectively　design　a　hybrid　metal　MOFs　photocatalyst　and　to　improve　the　full　utilization　of　photogenerated　electrons-holes　in　a　photocatalytic　process.　©　2022　Elsevier　Inc.