Thermally stimulated luminescence (TSL) measurements with spectral resolution on undoped NaI and NaI doped with Tl, In, and Eu are presented and analyzed. Based on the trap parameters extracted, carrier release rates are calculated as a function of temperature. The parameters calculated at 300 K by whole peak fitting yield release rates which are about 1−2 orders of magnitude higher than those obtained using the initial rise method. These data can be used to test release-rate predictions of the first ab initio calculations of carrier release and capture rates on dopants in NaI by Prange et al. A kinetic model of rate equations describing energy relaxation in NaI with different activators is used to simulate the TSL experiment and suggest an interpretation of the peaks' origin(s). We found that thallium can trap either charge carrier, electron or hole, while indium is only a hole trap, and europium induces very shallow electron traps in NaI.