1-Methylthio-1-phenyl-1-silacyclohexane 1, the first silacyclohexane with the sulfur atom at silicon, was synthesized and its molecular structure and conformational preferences studied by gas-phase electron diffraction (GED) and low temperature 13C and 29Si NMR spectroscopy (LT NMR). Quantum-chemical calculations were carried out both for the isolated species and solvate complexes in gas and in polar medium. The predominance of the 1-MeSaxPheq conformer in gas phase (1-Pheq:1-Phax = 55:45, ΔG° = 0.13 kcal/mol) determined from GED is consistent with that measured in the freon solution by LT NMR (1-Pheq:1-Phax = 65:35, ΔG° = 0.12 kcal/mol), the experimentally measured ratios being close to that estimated by quantum chemical calculations at both the DFT and MP2 levels of theory.