We present a systematic multiconfigurational study of the lowest two doublet potential energy surfaces of atomic aluminum with molecular oxygen. The most likely products, AlO and AlO2,are expected to figure prominently in subsequent reactions to form Al2O3. The main reaction pathways on both surfaces invariably lead to the formation of cyclic AlO2, possibly followed by isomerization to the lower-energy linear AlO2 isomer. A reaction path leading from Al+O2directly to AlO+O was not located. However, both AlO2 isomers can dissociate to AlO+Owith no barrier beyond endothermicity. There is also no barrier for the reaction of AlO2 with AlO to form Al2O3, and this reaction is highly exothermic. We present a systematic multiconfigurational study of the lowest two doublet potential energy surfaces of atomic aluminum with molecular oxygen. The most likely products, AlO and AlO 2 , are expected to figure prominently in subsequent reactions to form Al 2 O 3 . The main reaction pathways on both surfaces invariably lead to the formation of cyclic AlO 2 , possibly followed by isomerization to the lower-energy linear AlO 2 isomer. A reaction path leading from AlϩO 2 directly to AlOϩO was not located. However, both AlO 2 isomers can dissociate to AlOϩO with no barrier beyond endothermicity. There is also no barrier for the reaction of AlO 2 with AlO to form Al 2 O 3 , and this reaction is highly exothermic.