Molecular structures have been determined for perfluorodimethyl ether, perfluorodiethyl ether, perfluoromethyl perfluoroethyl ether, and model compounds for polyperfluorinated ethers. Optimized geometries, net charges, molecular orbital energies and plots, bond stretching force constants, vibrational frequencies, and infrared intensities are reported with use of ab initio SCF calculations. In addition, experimental, infrared spectra of perfluorinated ethers in argon matrixes and as neat films are compared with theoretical spectra. The data presented herein provide an excellent basis for understanding the structure of the ethers and assigning the infrared band centers. In addition, molecular mechanics is used to obtain insight for the catalytic behavior of the polymeric materials on metal oxide surfaces. © 1991, American Chemical Society. All rights reserved.