The electron paramagnetic resonance of Mn2+ in NaF single crystals is investigated at different temperatures from 573° K to 93° K. Four different spectra designated as I, II, III2 and III4 are observed. Spectrum I consists of a single broad resonance corresponding to precipitated Mn2+ ions. Spectrum II is isotropic and centred nearg = 2.00. This spectrum corresponds to substitutional Mn2+ ions with remote charge compensating sites and therefore with local cubic symmetry. Spectrum III2 withg = 2.014 and spectrum III4 withg = 1.995 are also due to substitutional Mn2+ ions but subjected to tetragonal crystalline fields and are the same as those reported by earlier workers. Superhyperfine structure has been observed in spectra II, III2 and III4. The analysis of that structure in spectra II and III2 has been carried out for the first time and the constants As, and Aσ are given. The spectra are analysed by the usual spin-Hamiltonian method.