Saturated hydrocarbons have structures with completely staggered bonds and dihedral angles of 180 degrees. Substituting hydrogen by fluorine results in a slight shift from 180 degrees, giving rise to a helical structure. X-ray diffraction Studies on fibers and computational Studies on perfluoroalkanes estimate a dihedral angle of about 17 degrees from the trails position. The rotational spectra of perfluoropentane and its three C-13 isotopomers have been observed and assigned using a pulsed-jet Fourier transform microwave spectrometer. The rotational constants for the parent species are A 990.6394(3) MHz, B 314.0002(1) MHz, and C 304.3703(1) MHz, respectively. The determination of in exact dihedral angle has been challenging, as the helical twist has proven to be quite sensitive to the structural inputs and constraints. A series of r(0) structures incorporating various model constraints and a Kraitchman analysis gives a range of 13-19 degrees for the torsional angle. An objective approach, which only assumes Overall C-2 symmetry, is to scale the principal coordinates from ab initio models by the square root of the ratio of the observed second moments to the computed second moments. The scaled structures Of Computed models at various levels of theory reproduce the parent second moments exactly and the C-13 second moments very well, giving a dihedral angle of 17 F from trans. The microwave spectrum Of perfluoropropane has also been observed and assigned. The rotational constants are A 1678.5982(9) MHz, B 900.1968(10) MHz, and C 955.3216(11) MHz, respectively. Unlike longer perfluoroalkanes, perfluoropropane has a nonhelical, C-2v, Structure. Computations are in excellent agreement with experimental results.