We present an unusual discrete P-Te anion, P4Te22-, which is readily obtained by the oxidation of white phosphorus with Te-2(2-) in N-methyl imidazole at ambient temperature. According to the P-31 and Te-125 NMR spectra, the anion P4Te22- had a bicyclo-[1.1.0]tetraphosphane ("butterfly") structure with the tellurium atoms in the exo positions. The anion was remarkably stable at ambient temperature and disproportionated only slowly with the formation of elemental tellurium. P4Te22- is the first P-Te anion with a bicyclo[1.1.0]tetraphosphane structure. When Se-2(2-) or S-2(2-) was reacted with white phosphorus, the analogous seleno-and thiophosphate anions P4Se22- and P4S22- were formed, thus completing the series of phosphorus-chalcogen anions P(4)Ch(2)(2-) (Ch = S, Se, Te). The synthesis of P4Te22- demonstrated that binary P-Te anions do exist as stable species in solution.