In this paper, we have reported a novel photocatalytic study of vanadium-doped SnO2 nanoparticles (SnO2: V NPs) in rhodamine B degradation. These NPs have been prepared with vanadium concentrations varying from 0% to 4% via the coprecipitation method. Structural, morphological, and optical properties of the prepared nanoparticles have been investigated by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscope (TEM), and UV-Vis and photoluminescence (PL) spectroscopy. Structural properties showed that both undoped and SnO2: V NPs exhibited the tetragonal structure, and the average crystal size has been decreased from 20 nm to 10 nm with the increasing doping level of vanadium. Optical studies showed that the absorption edge of SnO2: V NPs showed a redshift with the increasing vanadium concentration. This redshift leads to the decrease in the optical band gap from 3.25 eV to 2.55 eV. A quenching in luminescence intensity has been observed in SnO2: V NPs, as compared to the undoped sample. Rhodamine B dye (RhB) has been used to study the photocatalytic degradation of all synthesized NPs. As compared to undoped SnO2 NPs, the photocatalytic activity of SnO2: V NPs has been improved. RhB dye was considerably degraded by 95% within 150 min over on the SnO2: V NPs.