MOF-on-MOF　composites　are　deemed　promising　candidates　to　accomplish　synergistic　CO2　capture　and　photoreduction　thanks　to　their　plentiful　active　sites,　extended　light　response　range,　timely　separation　of　photoexcited　electron-hole　pairs,　and　large　CO2　adsorption　capacities.　Unfortunately,　the　controllable　growth　of　the　designed　MOF-on-MOF　heterostructure　is　challenging.　Deficient　interphase　contact　and　the　consequent　mass　transfer　deprivation　is　one　of　the　primary　obstacles　severely　impairing　the　catalytic　efficiency.　Herein,　the　contact　between　two　widely-employed　MOFs　of　Ni-BDC　and　NH2-MIL-125　was　significantly　strengthened　by　exploiting　a　self-assembled　array　of　Ni-BDC　microsheets.　In　contrast　to　the　spontaneously　formed　spheroidal　aggregate,　the　loosely-packed　array　exhibits　amplified　accessible　surfaces　to　interact　with　NH2-MIL-125,　contributing　to　a　radically　improved　interfacial　built-in　electric　field　and　7∼9　times　rises　in　the　product　yields.　Moreover,　the　preferably　thin　thickness　of　Ni-BDC　microsheets　prompts　its　macroscopic　flexibility,　permitting　intensified　deformation　for　enhanced　interphase　contact.　Coupled　with　the　additional　contribution　from　its　copious　Lewis　acid　sites,　the　developed　NH2-MIL-125@Ni-BDC　array　simultaneously　converted　CO2　into　CO　and　CH4　at　rates　that　cannot　be　matched　by　its　isostructural　Co　counterpart　with　declined　acidity　and　flexibility.　This　work　innovatively　reveals　the　immense　importance　of　morphology　tailoring　and　assembly　tactic　to　interphase　contact　modulation　and　the　upgrade　of　catalyst　performances.　©　2024　Elsevier　B.V.