AbstractThe Raman spectra of gaseous, liquid and solid 1,1,1,3,3,3‐hexafluoro‐2‐methoxypropane, (CF3)2CHOCH3, and the corresponding methoxy‐d3isotope, (CF3)2CHOCD3, together with the infrared spectra of the gases and solids, have been recorded from 3500 to 30 cm−1. A comparison of the vibrational spectra obtained for the fluid phases with those obtained for the amorphous and annealed solids indicates the predominance of a single conformer at ambient temperature in the fluid phases with the same conformer present in the solid state. Based on the lack of depolarized Raman lines in the fluid phases, and a predominance of nondescript infrared band contours, it is concluded that the stable conformer is thegaucheform which has the methoxy group rotated approximately 60° from eclipsing the secondary carbonhydrogen bond. Thirty‐eight of the 39 normal modes have been assigned based on group frequencies, isotopic shifts, depolarization values and infrared band contours. There appears to be coupling of the CF3and methoxy torsional modes. Utilizing a coupled‐top barrier calculation, the barrier to internal rotation of the perfluoromethyl groups is estimated to be 2858 ± 100 cm−1(8.2 ± 0.3 kcal mol−1) based on the torsional frequencies of 107 and 64 cm−1observed in the solid phase. Several of the fundamentals appear as doublets in the spectra of the solids, which indicates that there are at least two molecules per primitive cell. These results are compared with similar data for some