Here, we report features of YVO₄:Sm³⁺ nanocrystalline powders prepared via modified Pechini technique. Doping concentration effect on structural and luminescence properties has been studied in detail. XRD and Raman spectroscopy confirmed synthesis of single phase nanoparticles with no additional phase. SEM images showed that prepared nanophosphors have average size of 60 nm. Emission and excitation spectra of Sm³⁺-doped YVO₄ nanocrystalline powders consisted of the characteristic lines corresponding to the intra-configurational f-f transitions dominated by electric dipole ⁴G_5/2–⁶H_9/2 transition. The optimal Sm³⁺ doping concentration was found to be dependent on excitation mechanism. Concentration quenching in YVO₄:Sm³⁺ nanophosphors occurred via dipole–dipole interaction regardless of the excitation. Temperature effect on emission spectrum was investigated in terms of luminescence intensity and chromaticity coordinates. YVO₄:Sm³⁺ nanoparticles have potential application in ratiometric luminescence thermometry. ⁴G_5/2 lifetime gradually declined along with increase of Sm³⁺ ions amount.