The three-dimensional silver-selenoarsenate RbAg2As3Se6 is a kinetic product in the methanolo-thermal reaction between RbCl, AgBF4 and Li3AsSe3. It contains [As3Se6](3-) rings, connected by formal "Ag-2(2+)" dumb-bell units to form a three-dimensional framework structure (3)(infinity)[Ag2As3Se6](-). The ability of the Ag-2(2+) units to adapt an octahedral coordination environment of chalcogenide atoms is crucial for obtaining this unique framework. The Rb+ cations are coordinated in a crown-like manner by two [As3Se6](3-) rings and form polar columns [Rb(As3Se6)](2-).