The structures of two new salts of the P2Se64- anion, [(py(2)Li)](4)[P2Se6] center dot 2py and [pyH](4)[P2Se6] center dot H2O, prepared using a new synthetic route in solution starting from easily available educts, are presented. The salts are characterized also in solution by means of multinuclear (P-31, Se-77, Li-7) NMR spectroscopy. The P-31 and Se-77 NMR spectrum of the waterstable P2Se64- anion are discussed in detail for the first time. The chemical shift of the P2Se64- anion in the Li+ salts depends strongly on the solvent used. Remarkably, the newly synthesized salts are stable in water.