A series of luminescence Ba3(VO4)2 nanoparticles doped with Sm3+ ions, known as a potential candidate for luminescence thermometry, was synthesized using the modified Pechini method. Morphological, structural, and optical properties of the particles were thoroughly characterized, and the sample with a concentration of 2 at.% was selected as the optimal candidate for the luminescence thermometry studies. The diverse thermal responses of the excitation spectra enable multimode temperature sensing, utilizing the spectral position, bandwidth, and luminescence intensity ratio between the charge transfer band and Sm3+ transition. This approach allows for accurate temperature measurements across a broad range (98 – 873 K), achieving a relative thermal sensitivity of up to 1.6% K−1 at moderate temperatures.