Generally, the electronic stability of aluminum clusters is associated with either closed electronic shells of delocalized electrons, or aluminum in the +3 state. To explore alternative routes for electronic stability in aluminum oxide clusters, theoretical methods were used to examine the geometric and electronic structure of AlnOm (2≤n≤7; 1≤m≤10) clusters. Two types of electronically stable clusters with large HOMO-LUMO gaps were identified the first being Al2nO3m clusters with a +3 oxidation state on the aluminum, and the second being planar clusters such as Al4O4, Al5O3, Al6O4, and Al6O5. The structures of the planar clusters have external Al atoms bound to a single O atom. Their electronic stability can be explained by the multiple valence Al sites with the internal Al atoms having an oxidation state of +3, while the external Al atoms have an oxidation state of +1. The formation of AlnOm+ clusters with high concentrations of oxygen were found experimentally. To determine the stability of such clusters theoretical methods were used to examine the geometric and electronic structure of these clusters (2≤n≤7; 1≤m≤10). The structures were found to be below average in terms stability, implying formation in a low collision environment.