Eu³⁺ doped red emitting phosphors of formulae KSrLa_1-y(PO₄)_x(VO₄)_2-x:yEu³⁺ (where x = 0, 1 and 2 and y = 0, 0.02, 0.05, 0.10 and 0.015) were synthesized by a high temperature solid state reaction route. The compounds were characterized by a powder XRD method, and a complete structure determination for KSrLa(PO₄)(VO₄) was carried out using the Rietveld refinement method. The compound crystallized in the rhombohedral system with space group (R%3m). The structure of the compound shows that La³⁺ is occupied at two positions, namely, trigonal antiprism (six coordinated) and truncated hexagonal bipyramidal (10 coordinated) centres, with occupancy of 0.94 and 0.06, respectively. The effect of vanadium substitution on excitation and emission spectra of the compounds was investigated using time resolved photoluminescence spectroscopy (TRPLS). The lifetimes of ⁵D₀→ ⁷F₂ transition were determined for all the compounds, which are in agreement with emission spectroscopic results. Judd–Ofelt analysis of the compounds clearly shows that the more polarized environment around Eu³⁺ in the case of the vanadate and phosphovanadate in comparison to the phosphate leads to more colour purity of the emission, when excited by UV light.