The p-Si(or n-Si)/GeO[SiO2] (or GeO[SiO])/indium-tin-oxide (ITO) structures were fabricated by simultaneous evaporation of GeO2 and SiO2 (or SiO) powders in high vacuum and further deposition of ITO contacts using the magnetron sputtering technique. The structural properties of the GeO[SiO2] and GeO[SiO] films were studied using FTIR and Raman spectroscopy. According to Raman data, the GeO[SiO] films deposited at a temperature of 100 °C contain amorphous Ge clusters. Their current-voltage characteristics were measured in the air atmosphere, and resistive switching (memristor effect) was observed in structures without a preliminary forming procedure. The Shklovskii-Efros percolation model gives a consistent explanation for the charge transport in the high-resistive state and the low-resistive state of memristors based on GeO[SiO2] or GeO[SiO] films.