The aqueous solutions of xMePO₃ · (1 - x)MeF glasses (Me = Li, Na) containing ≃2.5 mol % MeF are investigated by two-dimensional homonuclear correlation ³¹P-³¹P NMR spectroscopy and by high-resolution ¹⁹F NMR technique. The anionic composition of products is found, and the NMR parameters of the anionic network fragments are determined for the glasses studied. The quantitative distribution of fluorine over the corresponding fluorine-containing anions is obtained, and the effect of the cation component of glass network on this distribution is demonstrated.