We propose a complex model of local anode oxidation of metals taking into account the processes occurring in the probe-substrate system in dry air, in water vapor, and in the water film adsorbed on the sub strate surface. It is shown that local anode oxidation occurs due to generation of oxygen ions as a result of decomposition of water molecules in an electric field; the predominant source of oxidizer is the film of water adsorbed on the substrate surface. The results of numerical simulation of local anode oxidation of titanium demonstrate good correlation with experimental dependences of the height of oxide nanostructures on the duration of local anode oxidation, which confirms the effectiveness of the proposed model. Our results can be used in the development of technological processes of formation of elements of nanoelectronics by local anode oxidation.