A series of 5-alkyl/aryl-1,3 lambda(4)delta(2),2,4,5-dithiadiazarsoles RAs(S2N2) (R = Me, Et, Pr-i, Bu-t, Ph, Mes) were prepared by a ligand exchange between [(Bu2Sn)-Bu-n(S2N2)](2) and the corresponding organodihalogenoarsines RAsX2 (X = Cl, I). All products were characterized by NMR, IR, and Raman spectroscopies and mass spectrometry. The crystal structures of the aryldithiadiazarsoles (R = Ph, Mes) were determined.