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　onestep　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]center　dot　2[Zn(Im)4]center　dot　2Im　(AlOC-121,　H3L　=　2,3-dihydroxybenzoic　acid,　Cat　=　catechol　Im　=　imidazole)　and　[Al4(L)4(Cat)2]center　dot　2[Fe(Im)6]center　dot　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.