The extraction in ethylenediamine (en) of "AsSe4", "TlAsSe4", and "InAsSe4", followed by reaction with cation sources or 2.2.2-cryptand, has led to the isolation of [NEt4](2)[As2Se6] (1), [enH][AsSe6]. 2.2.2-cryptand (2) : [NEt4][AsSe8] (3), and [(en)(2)In(SeAs(Se)Se-2)]. en (4). These compounds contain AsSe+ units coordinated to Se-2(2-), Se-5(2-), and Se-7(2-) ligands in 1 and 4, 2, and 3, respectively. The [As2Se6](2-) anion features two AsSe+ units joined by Se-2(2-) ligands; the resultant As2Se4 ring exhibits a chair conformation. The [AsSe6](-) anion features an AsSe+ unit coordinated in a bidentate fashion by a Se-5(2-) ligand to create an AsSe5 ring with a chair conformation. The [AsSe8](-) anion contains an AsSe+ unit coordinated by a bidentate Se-7(2-) ligand; the resultant AsSe7 ring has a crown conformation. [(en)(2)In(SeAs(Se)Se-2)] features an octahedral in atom bridged by one Se2- and one Se-2(2-) ligand to an AsSe+ unit; two bidentate en ligands complete the coordination about the In center.