Photocatalysis is regarded as one of the most environmentally benign methods of mitigating the effects of textile wastewater. Despite the fact that various semiconducting metal oxides are used in photocatalysis, their performance is still insufficient. In this study, the hydrothermal method was used to synthesize rare-earth (RE) elements [Holmium (Ho) and Ytterbium (Yb)] doped vanadium pentoxide (V2O5) to improve its photocatalytic efficiency. The effect of RE ions on the photocatalytic efficiency of doped V2O5 has also been analyzed from both the experimental and first-principle density functional theory (DFT) methods. The stable orthorhombic crystal structure of doped V2O5 is confirmed by the X-ray diffraction with no secondary phase, and high-stressed conditions are generated for the 3 mol.%. The crystallite size, strain, and dislocation density are calculated to perceive the doping effect on the bare V2O5. The optical characteristics have been measured using UV–vis spectroscopy. The absorptions are found to be increased with increasing doping concentrations; however, the bandgap remains in the visible range. The photocatalytic properties are examined for the bare compound with varying pH, with the highest efficiency exhibited for pH 7. Moreover, it is observed that the RE ions significantly impact the catalytic behavior of V2O5. The degradation efficiency is improved by 93 % and 95 % for the 3 mol.% of Ho and Yb-doped V2O5 samples within 2 h, respectively, and the mechanism behind these extraordinary efficiencies has been explained thoroughly.