The local structure of P-rich and Se-rich phosphorus-selenium glasses was studied using high-resolution (31)P solid-state MAS NMR. Two-dimensional (31)P homonuclear through-bond correlation MAS experiments and 2D homonuclear J-resolved MAS measurements were performed at high spinning frequency to probe P-P and P-Se-P connectivities between the different P sites for the compounds in two glass-forming regions, P(2.5)Se(97.5)-P(50)Se(50) and P(67)Se(33)-P(84)Se(16). Amorphous phosphorus and crystalline alpha-P(4)Se(3) and beta-P(4)Se(3) were also studied as reference materials. Glasses from the Se-rich region contain mainly three- and four-coordinated P sites linked together by Se(n) chains, whereas P-rich glasses contain a mixture of P(4)Se(3) molecular units and possibly other structural units embedded in a red-phosphorus-like polymeric network.