The photoluminescent properties of NaIn(WO4)(2) are enhanced remarkably by doping bismuth in the position of indium. Temperature-dependent photoluminescence (PL) spectra have been detected to illustrate the effects of doping bismuth on the PL of NaIn1-xBix(WO4)(2). At low temperatures, a possible sensitization mechanism of bismuth is the energy-transfer process of the dipole-dipole interaction between Bi3+ and the W-O group because electrons could hardly pass over the energy barrier between them. As temperatures rise, the electrons can pass over the barrier, and then the charge-transfer process performs more effectively. The analysis of the temperature-dependent PL results has shown that the energy barrier is 0.17 eV. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3417080] All rights reserved.