Glasses in the system [Na2S]2/3[(B2S3)x(P2S5)1–x]1/3 (0.0 ≤ x ≤ 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and 11B, 31P, and 23Na high resolution solid state magic-angle spinning (MAS) NMR techniques. 31P MAS NMR peak assignments were made by the presence or absence of homonuclear indirect 31P–31P spin–spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B–S–P connectivity in the glassy network was quantified by 31P{11B} and 11B{31P} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74–, pyrothiophosphate, Na/P = 2:1, units into PS43–, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B–S–B. Detailed inspection of the 11B MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2 groups all the way to the fully depolymerized orthothioborate (BS33–) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (Tg) and ionic conductivities can be rationalized. Up to x = 0.4, the dominant process can be described in a simplified way by the net reaction equation P1 + B1 P0 + B4, where the superscripts denote the number of BS atoms for the respective network former species. Above x = 0.4, all of the thiophosphate units are of the P0 type and both pyro- (B1) and orthothioborate (B0) species make increasing contributions to the network structure with increasing x. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B–S–P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.