A novel phosphor of Glaserite type Orthovanadate K3Y[VO4]2 substituted with the trivalent rare-earth Sm3+ ions were synthesized by the conventional high temperature solid-state reaction method, their structural characterization and photoluminescent properties were investigated by X-ray diffraction and spectrofluorimetry. The phase-purity of glaserite structure in the synthesized compound was verified by XRD study. The morphology was measured by FESEM. Host lattice emits broad-band green color and it is originated from the [VO4]3−. Photoluminescence studies of Sm3+ activated samples show orange red emission. The charge transfer behaviours from [VO4]3− to Sm3+ ions (host to activator) in K3Y(1−x)[VO4]2: xSm3+ phosphors have been confirmed by photoluminescence and PL decay life time measurement. No concentration quenching was observed even for higher concentration of the dopant Sm3+ ions. The CIE chromaticity color coordinate values were calculated and it is very much closer to the NTSC standards. All the results clearly indicate that self-activated K3Y1−x[VO4]2 with the rare earth xSm3+ activated phosphors show great potential as a phosphor material for near-UV based white LEDs.