The one- and two-electron oxidation reactions of tetrathiolated di-tert-butylpyrene compound 1 with NO[Al(ORF)(4)] (ORF = OC(CF3)(3)) resulted in radical cation salt 1(center dot+)[Al(ORF)(4)](-) and diradical dication salt 1(2+center dot center dot)center dot 2[Al(ORF)(4)](-), respectively. Both salts were isolated as stable crystals and investigated by single-crystal X-ray diffraction, EPR spectroscopy, SQUID measurements, and UV-vis spectroscopy. The electron spin density is delocalized on one single sulfur-doped ring in 1(center dot+) and on both sulfur-doped rings in 1(2+center dot center dot). The diradical dication 1(2+center dot center dot) features a robust triplet ground state, representing the first example of a high-spin sulfur-hydrocarbon diradical.