Nanometric V-doped particles with vanadium concentration varying from 0 to 10% were prepared using the polyol method. The influence of the doping on the textural, structural and optical properties was studied by various methods of characterization. X-ray diffraction (XRD) patterns disclose that nanocrystallites of cassiterite, i.e. rutile-like tetragonal structure SnO2 and the absence of a new vanadium phase in the XRD pattern in the different concentration of doping were formed after annealing, the ordinary crystallite size decreased from 20.6 to 12.3 when the doping concentration increased from 0 to 10%, respectively. Moreover, the N2 sorption porosimetry and transmission electron microscopic show that all samples synthesized were constituted of an aggregated network of almost spherical nanoparticles, which sizes changed with the altitude in the doping concentration to 10%. In accordance with UV–visible absorption measurements, this diminution of nanoparticles sizes was followed by a decrease in the band gap value from 3.25 eV, for undoped SnO2, to 2.75 eV, for SnO2 doped at 10%. On the other part, the photocatalytic activity of undoped and V-doped SnO2 nanoparticles was studied using methylene blue (MB) as model organic pollutants. The SnO2 nanoparticles doped at 10% of vanadium disclosed that the discoloration of MB reached 97.4% after irradiation of 120 min, with an apparent constant rate of the degradation reaching 0.035 min−1 for MB degradation that was about 2.5 times more than that of pure SnO2 (0.014 min−1).