Thermally stimulated luminescence (TSL) of Na2ZnCl4 single crystals showed three glow peaks having their peak maxima at 343, 425 and 475 K. Optical absorption (OA) data of unirradiated samples revealed an absorption band at 272 nm while X-irradiation caused additional bands at 462 and 723 nm. Growth and room temperature annealing studies of TSL and OA supported the idea of attribution of 425 K glow peak and 462 nm absorption band to F-centres. The 272 nm OA band is due to Zn2+ centres whereas the 723 nm absorption band and 475 K glow peak have been assigned to Zn+ centres.