Relative permittivity measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) in the liquid phase are reported. Measurements were performed by using a direct capacitance method at temperatures from 223 K to 303 K and pressures up to 16 MPa for HFC-227ea and HFC-236ea and at temperatures from 263 K to 303 K up to 16 MPa for HFC-365mfc. The uncertainty of the relative permittivity measurements is estimated to be better than ±1.1·10-2. The theory developed by Vedam et al., and adapted by Diguet, and the Kirkwood modification of the Onsager were applied to obtain the apparent dipole moment of HFC-227ea, HFC-236ea, and HFC-365mfc in the liquid state, found to be 2.356 D for HFC-227ea, 2.624 D for HFC-236ea, and 4.917 D for HFC-365mfc. The effective dipole in the liquid state of HFC-236ea predicted by the Kirkwood−Frölich theory is 2.065 D. Density functional and density functional self-consistent calculations (SCIPCM) of the electronic distribution and of the dipole moment are reported for HFC-227ea.