Abstract The infrared spectra of ethylmethylfluorosilane (CH 3SiHFCH 2CH 3) have been recorded as a vapour, liquid and solid at 78 K in the 4000–50 cm −1 range and isolated in an argon matrix at ca. 5 K. Infrared spectra of two different solid phases were obtained after annealing to temperatures of 120 and 130 K, and recooling to 78 K. Although the IR spectra were quite similar in the MIR region, certain differences were noted in the FIR region below 400 cm −1. The most stable conformer MeMe was present after annealing to 130 K, but three bands belonging to MeH were detected after annealing to 120 K. Various infrared bands changed intensity when the argon matrix was annealed to temperatures between 20 and 35 K, and some of these were related to changes in the conformational abundance. Raman spectra of the liquid were recorded at room temperature and at various temperatures between 295 and 153 K. Spectra of an amorphous and annealed solid were recorded at 78 K. In the variable temperature Raman spectra, various bands changed in intensity and were interpreted in terms of conformational equilibria between the three possible conformers. Complete assignments were made for all the bands of the most stable conformer MeMe. From various bands assigned to the three conformers, the conformational enthalpy difference Δ H from MeMe to the intermediate energy conformer MeH was found to be 0.5 kJ mol −1 and to the highest conformer MeF was 0.7 kJ mol −1. At ambient temperature this leads to 39% MeMe, 32% MeH and 29% of the MeF conformer in the liquid. Ab initio calculations in the RHF, MP2, DFT approximations and very accurate G2 calculations were carried out. With one exception, the MeMe conformer had the lowest enthalpy in all these calculations, the MeH had the intermediate and the MeF the highest enthalpy, and the calculations were in good agreement with the measurements.