The ammoxidation of toluene was studied both in presence and absence of gaseous oxygen over MoO3 and in situ prepared Mo4O11 (orth.) and MoO2. Irrespective of the partial pressure of oxygen, total reaction rates decrease in the following order: MoO3 > Mo4O11 > MoO2. The corresponding sequence for the selectivity towards formation of benzonitrile was found to depend on the partial pressure of oxygen. In two phase samples, no synergistic effects were observed for the formations of nitrile and carbon oxides. A comparison of rates for selective and nonselective products obtained in presence of gaseous oxygen with those obtained in its absence yield information as to whether the various products are formed at identical or different crystal faces. In the case of MoO3, nitrile and carbon oxides were found to be competitively formed at the same faces, while over MoO2 they are formed at different faces. Both options seem to prevail on Mo4O11.