Photo- and thermoluminescence (TL) spectra of NaLaF4:Ln3+ (Ln = Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm) and NaLaF4:Ce3+, Ln3+ (Ln = Nd,Sm,Ho,Er,Tm) are presented and used together with the empirical Dorenbos model in order to establish the 4f energy level positions of all tri- and divalent lanthanide ions doped in NaLaF4. The information will be presented in the form of an energy level diagram. It is shown that in addition to this diagram only two assumptions, viz., the presence of two host related electron traps and the presence of Vk-centers, are necessary for explaining the lanthanide-specific TL glow curves of both Ln mono- and Ce–Ln codoped NaLaF4.