Two novel perthiophosphonic acid anhydrides, 2,4-bis(R x,y)-1,3-dithia-2,4-diphosphetane 2,4disulfide [(R x,y-P(S)S)2; R x =3-methoxytolyl (SAV-B1) and R y =2-methoxytolyl (SAV-B2)] were synthesized. From the reaction of SAV-B1 and SAV-B2 with alcohols, four new dithiophosphonic acids [HS2P(R x,y)(ORn)] (Rn; R1=ethyl R2=2-propyl) were prepared. These acids were converted to corresponding ammonium salts, [NH4][S2P(R x,y)(ORn)]. The ammonium salts were further reacted with NiCl2.6H2O to prepare four new dithiophosphonato nickel(II) complexes, [Ni(S2P(R x,y)(ORn))2]. The ligands and complexes were characterized by elemental analyses, IR, ESI-MS, 1D 1 H, 13 C, 31 P NMR and 2D HSQC techniques. Complementary structural information was provided by the HSQC spectrum of the [NH4][S2P(R x,y)(OR2)]. The structure of the perthiophosphonic acid anhydrides was deduced from the structures of dithiophosphonates thereof.