Insights into the structure and dynamics of the binary As-Se glass system have been obtained from high-temperature Se-77 nuclear magnetic resonance (NMR) studies of molten samples. In materials having As contents < 20 at.%, dynamic exchange averaging processes are detected and analysed quantitatively by detailed lineshape simulations. At high-temperatures (1.5 x glass transition temperature), only a single averaged Se-77 NMR signal is observed, whose chemical shift arises from the quantitative distribution of As-Se and Se-Se bonds. A detailed analysis of the compositional dependence reveals a tendency towards chemical ordering, based on the structurally dominant AsSe3/2 groups. Furthermore, the experimental data serve to differentiate between various intermediate range ordering scenarios and favor a structural description in terms of a network in which AsSe3/2 and Se-2/2 groups are randomly linked. (C) 2001 Elsevier Science B.V. All rights reserved.