A comprehensive multinuclear ( 7 Li, 31 P, 35 Cl, 77 Se, 79 Br) nuclear magnetic resonance (NMR) study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically disordered solid solutions of composition Li 6 PS 5− x Se x X (0 ≤ x ≤ 1, X = Cl, Br) with the Argyrodite structure. In contrast to the situation with the corresponding iodide homologs, there is no structural ordering between the 4a and 4 c sites, with the halide ions occupying both of them with close to statistical probabilities. Nevertheless, throughout the composition range, the 16e Wyckoff sites of the Argyrodite structure are exclusively occupied by the chalcogen atoms, forming PY 4 3− (Y = S, Se) tetrahedra, indicating the absence of P-halogen bonds. 31 P magic-angle spinning (MAS)-NMR can serve to differentiate between the various possible PS 4− n Se n 3− tetrahedral units in a quantitative fashion. Compared to the case of the anion-ordered Li 6 PS 5− x Se x I solid solutions, the preference of P–S over P–Se bonding is significantly stronger, but it is weaker than in the halide free solid solutions Li 7 PS 6− x Se x . Each individual PS 4− n Se n 3− tetrahedron is represented by a peak cluster of up to five resonances, representing the five different configurations in which the PY 4 3− ions are surrounded by the four closest chalcogenide and halide anions occupying the 4c sites; this distribution is close to statistical and can be used to deduce deviations of sample compositions from ideal stoichiometry. Non-linear 7 Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS 4− n Se n 3− ions ( n ≤ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e., selenium-richer PY 4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li + ions to spend on average more time near them. Temperature dependent static 7 Li NMR linewidths indicate higher mobility in the present systems than in the previously studied Li 6 PS 5− x Se x I solid solutions. Unlike the situation in Li 6 PS 5− x Se x I no rate distinction between intra-cage and inter-cage ionic motion is evident. Lithium ionic mobility increases with increasing selenium content. This effect can be attributed to the influences of higher anionic polarizability and a widening of the lithium ion migration pathways caused by lattice expansion. The results offer interesting new insights into the structure/ionic mobility correlations in this new class of compounds.