The　aqueous　solution　chemistry　of　Al(III)　is　an　important　subject　in　the　fields　of　environmental　chemistry,　geochemistry　and　coordination　chemistry.　However,　aluminum　oxo　clusters　were　generally　isolated　by　the　one-step　synthesis　method.　In　this　paper,　we　developed　a　stepwise　assembly　synthesis　strategy　and　successfully　prepared　two　heterometallic　aluminum　oxo　clusters.　[Al4(L)4(Cat)2]·2[Zn(Im)4]·2Im　(AlOC-121,　H3L　=　2,3-dihydroxybenzoic　acid,　Cat　=　catechol　Im　=　imidazole)　and　[Al4(L)4(Cat)2]·2[Fe(Im)6]·2Im　(AlOC-122).　Single　crystal　structure　analysis　shows　that　they　are　unprecedented　structure　types,　where　aluminum　oxo　cluster　precursor,　metal　complexes　and　guests　co-crystallizing　in　one　structure.　These　compounds　were　fully　characterized　and　magnetic　properties　were　also　studied.　©　2021