[en] A malic acid assisted sol–gel route was successfully employed to prepare two distinct series of green emitting Ca₃V₂O₈ phosphors. In the first series, Tb was solely doped whereas in the second series Na and Tb were doped simultaneously in the Ca₃V₂O₈ crystal lattice. X-ray diffraction studies proved the utility of adopted preparative method by confirming the monophasic formation of all compounds from both the series. Spectral analysis like Raman spectroscopy, UV-DRS were undertaken to analyse the local structure, crystallinity and absorptive characteristics. XPS validated the presence of desired oxidation states of all the elements present. Finally, photoluminescence studies were done to elucidate the scope of prepared compounds as green emitting phosphors and also to understand the effect of both doping schemes on the luminescence. Intense green emission was observed in both the cases. Tb concentration of 0.08 was found to be optimum in case of Tb singly doped compounds whereas Tb = 0.12 showed highest intensity among the Na–Tb co-doped samples. Moreover, a red shift in the excitation wavelength was observed after Na doping signifying a change in the local electronic environment which in turn has affected the luminescence pattern. Local crystallinity and vacancy concentrations were found to have a major say on the emission intensities. (paper)