A description of the volumetric behaviour of segregated hydrofluoroethers has been carried out using PC-SAFT EOS. Characteristic parameters for several molecules were calculated where experimental data were available, and accurate results were obtained for compressed and saturated liquid density estimation, as well as for saturation curves. A functional group contribution scheme is proposed also for the calculation of the mentioned PC-SAFT EOS characteristic parameters, and this approach reproduces adequately the dependence on molecular structure of the parameters calculated in this work, and also gives good estimations when the parameters are extrapolated for other molecules of the same family.