In this study, the synthesis of zirconia as well as zirconia enriched with vanadium by modified sol-gel method was presented. The modification of the method was based on the replacement of the traditional basic promoter of hydrolysis, which is ammonia, with sodium hydroxide solution. The most favorable conditions for the synthesis of zirconium with a new hydrolysis promoter were selected. A comparative analysis of ZrO2 obtained using various hydrolysis promoters was performed. Both materials exhibited almost the same physicochemical properties, which proves that in this case the nature of the hydrolysis promoter used in sol-gel route does not significantly affect the properties of the ZrO2. Then, synthesis of ZrO2/V systems was carried out using model and real solutions containing vanadium ions as hydrolysis promoters. The solutions formed after vanadium catalyst leaching were used as real solutions. The effect of vanadium concentration and the presence of impurities on the final physicochemical properties of the obtained hybrid materials were investigated via scanning electron microscopy (SEM), dynamic light scattering (DLS), energy-dispersive X-ray microanalysis (EDS), Fourier transform infrared spectroscopy (FT-IR), low-temperature nitrogen sorption (BET), thermogravimetric analysis (TGA). The analysis of the obtained results allows to state that the developed technique for the synthesis of ZrO2 and ZrO2/V systems, using a modified sol-gel method, enabled the production of attractive materials.