A Cu-doped NaLi2PO4phosphor material was successfully synthesized through the high-temperature solid state diffusion method. It was mainly doped with Cu2Cl2and CuCl2salts for impurities in the form of Cu+and Cu2+, respectively. Formation of the material in the single phase of the phosphor material was confirmed by powder XRD. Morphological and compositional characterization was done using XPS, SEM and EDS techniques. The materials were annealed in reducing, (10% H2in Ar) and CO/CO2(by burning charcoal in a closed system), as well as in oxidizing (air) atmospheres at different temperatures. ESR and PL studies were conducted for studying redox reactions due to annealing and its effect on TL characteristics. It is known that the impurity Cu could exist in Cu2+, Cu+and Cu0forms. The material was doped with two different salts (Cu2Cl2and CuCl2) as sources of the impurities in two different formsi.e., Cu+and Cu2+, however, it was found that it gets incorporated in both the forms inside the material. Also, annealing in different atmospheres not only changed their ionic states but also affected the sensitivity of these phosphors. It was observed that at ∼10 Gy, NaLi2PO4:Cu(ii) is around 3.3 times, 3.0 times and almost equally sensitive than commercially available TLD-900 phosphor on annealing in air, 10% H2in Ar and CO/CO2at 400, 400 and 800 °C, respectively. However, NaLi2PO4:Cu(i) becomes 1.8 times sensitive after annealing in CO/CO2at 800 °C as compared to TLD-900. With high sensitivity, both the materials NaLi2PO4:Cu(ii) and NaLi2PO4:Cu(i) are good candidates for radiation dosimetry with a wide dose response (mGy–5.0 kGy).