SiO2-La2O3 binary oxide system was prepared by the sol-gel method without addition of strong polar solvents (e.g. water, alcohol) to the initial system. Changes in the surface and gel network structure were described as a function of the type and concentration of the second component that is lanthanum oxide. A series of samples with Si to La molar ratios of 1:0.1, 1:0.25, 1:0.5, and 1:1 were characterised by XRD, TG-TA, FTIR, and low-temperature nitrogen adsorption measurements. Results of the investigation showed that higher amounts of the lanthanum component in the binary oxide gel system led to a completely changed morphology of the porous structure of the surface gels obtained in a non-aqueous medium.