A novel blue emitting glaserite type α-Na3Y(VO4)2 nanocrystals substituted with the trivalent thulium ions were synthesized for the first time via citrate based solution combustion method. The monoclinic structure and well dispersed spherical morphology of the synthesized nanocrystals were confirmed by XRD, TEM, HRTEM and SAED analysis. Host lattice emits broad band blue color and it originates from the VO43−. The presence of a very intense and broad charge transfer band in excitation spectra of α-Na3Y(VO4)2:Tm3+ monitored under 474 nm demonstrates the efficient energy transfer from VO43− to Tm3+ in α-Na3Y(VO4)2:Tm3+. Photoluminescence studies of Tm3+ activated α-Na3Y(VO4)2 samples show blue emission under excitation wavelength 310 nm. The optimal doping concentration of Tm3+ ions in α-Na3Y(VO4)2 phosphors is found to be around 1.5 mol % and the major mechanism for concentration quenching is the dipole - dipole interaction. The quantum yield for the sample with optimum concentration is measured to be 18.16%. The CIE chromaticity color coordinates were calculated and it is very much closer to the NTSC standards with high color purity. The lifetime of the thulium characteristic blue emission is found to be in the order of 0.1 ms. All the results clearly indicate that pure α-Na3Y(VO4)2 as well as rare earth Tm3+ activated α-Na3Y(VO4)2 nanocrystals can be used as potential candidates in the field of optoelectronics, especially for the fabrication of near-UV based white LEDs, bio-imaging and labeling etc.