Cationic [W6S8L6]PF6 (L = PEt3 (3), 4-tert-butylpyridine (4)) clusters, were successfully synthesized and isolated for the first time by reacting the corresponding neutral W6S8L6 (L = PEt3 (1), 4-tert-butylpyridine (2)) clusters with [Cp2Fe]PF6 as the oxidant. The products 3 and 4 were characterized by NMR spectroscopy. mass spectroscopy, and X-ray crystallography (only for 3) and shown to be the desired oxidized W6S8 clusters with a metal electron count of 19. Magnetic property studies showed that they an paramagnetic compounds with S = 1/2. Their chemical properties and stability are also reported. Crystal data for 3 . 2THF: space group, R3 (No. 148); a = 13.91170(10) Angstrom; c = 32.4106(2) Angstrom; Z = 3.