The stable sulfur-substituted tetrahedrane derivatives 2-4 were synthesized by the reaction of tris(trimethylsilyl)tetrahedranyllithium 1 with diphenyl disulfide, bis(4-nitrophenyl) disulfide, and bis(2,4-dinitrophenyl) disulfide, respectively, and characterized by both NMR spectroscopy and X-ray crystallography. Phenylsulfonyltetrahedrane 5 was prepared by the reaction of 2 and m-chloroperbenzoic acid. The UV vis absorption spectra of 2-4 suggested an interaction of the a orbital of the tetrahedrane core and the lone-pair electrons on the sulfur atom, whereas no interaction for 5 was found. Thermal reactions of 2 and 5 are also reported; 2 underwent fragmentation into two acetylene molecules, whereas 5 gave the corresponding cyclobutadiene.