Rare‐earth vanadates of the form REVO4 (RE = Y, La, Gd, and Lu) doped by Yb3+/Ho3+, Yb3+/Er3+, or Yb3+/Tm3+ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln3+ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO4 and tetragonal YVO4, GdVO4, or LuVO4 doped by Ln3+ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb3+ ions and emitting ions.