In this work, we demonstrate the photoluminescence enhancement in a series of solid solutions, Ca0.9-xNa0.05YxMo1-xVxO4:Eu-0.05(3+) (x = 0.1, 0.3, 0.5) and Ca0.9-yNa0.05BiyMo1-yVyO4:Eu-0.05(3+) (y = 0.1, 0.3, 0.5), synthesized by solid-state reaction. By introducing BiVO4 or YVO4, the host lattice absorption and excitation of CaMoO4:Eu3+ in the near-UV region are enhanced arising from the decrease in the bandgap. The emission at 616 nm of Eu3+ under 365 nm excitation has been significantly improved. The emission of 616 nm reaches its maximum when the BiVO4 concentration equals to 3 atom %. The results reveal that modulating the band structure of a phosphor is an effective method to enhance the photoluminescence and to develop a suitable phosphor for near-UV light emission diode. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3240199]