The structures of the new compounds [Cu8(Ph2As2Se2)2(PhAsSe2)2(dppm)4] (1) (dppm = bis-diphenylphosphinomethane), [Cu4(Ph2As2Se2)2(PPh3)4] (2), [{K(18-crown-6)}2(PhAsSe3)] (3), [Na12(PhAsSe3)6(15-crown-5)6] (4) and 1/x[Na2(PhAsSe3)(thf)(H2O)3]x (5) are reported. 2-5 were prepared by reactions of metal thiolates with [(PhAs)2(mu-Se)(mu-Se2)].