Solar cells fabricated on the basis of semiconductor–insulator–semiconductor (SIS) structures have been obtained by deposition of transparent conductive ITO films onto silicon crystal substrates by the spray pyrolysis technique. Such structures may be considered as Schottky diodes with a thin insulating SiO2 layer at the interface formed during the ITO layer deposition. The examination of the current–voltage characteristics shows that, in n ITO/SiO2/nSi structures, there are two mechanisms of the direct current flow: (i) tunneling–recombination at direct voltages less than 0.3V and (ii) over barrier emission at voltages higher than 0.3V. In the first case, the direct current flow can be interpreted as multistep tunneling–recombination transitions of electrons from the silicon conduction band into the ITO conduction band with the number of steps being about 100. In the second case, the height of the potential barrier at the ITO–Si interface calculated from the I–V characteristics is about 0.65–0.68 eV.