Present　herein　is　the　currently　largest　catecholato-based　aluminum　oxo　clusters.　By　adjusting　the　amount　of　auxiliary　3,　5-dimethylpyrazole　ligands,　the　synthesis　of　aluminum　oxo　clusters　(AlOCs)　(AlOC-86)　to　high　nuclearity　AlOCs　(AlOC-88)　were　successfully　achieved.　Such　synthetic　strategy　is　applicable　to　imidazole　ligands　and　new　compounds　(AlOC-87　and　AlOC-89)　were　obtained.　Single　crystal　analysis　shows　that　AlOC-86　and　AlOC-87　are　hexanuclear　clusters　made　up　of　two　edge-sharing　tetrahedral　clusters.　The　nuclearity　of　compounds　AlOC-88　and　AlOC-89　is　doubled　and　they　are　S-shape　dodecanuclear　AlOCs.　The　aggregation　of　such　clusters　is　attributed　to　the　labile　sites　on　the　two　ends　of　the　hexanuclear　clusters.　In　addition,　open　aperture　(OA)　Z-scan　measurements　results　indicate　that　these　compounds　exhibit　manifest　reverse　saturation　absorption　(RSA)　response.