High pressure vapour-liquid equilibrium (HPVLE) data for binary systems consisting of either HFP or HFPO with toluene, carbon dioxide, hexafluroethane (R116) and dichlorotrifluoroethane (R123) were measured isothermally at 273.15 K and 313.15 K and pressures ranging up to 4 MPa. Two experimental methods were used for the measurements: a static synthetic method using a Pressure-Volume-Temperature (PVT) apparatus for the systems containing toluene with either HFP or HFPO and a static analytic method using the patented ROLSITM samplers for the systems containing R116, CO2 and R123 with either HFP or HFPO. Pure component vapour pressures for components HFP and HFPO were also measured using the static analytic apparatus over a narrow temperature range of interest. The experimental data was modelled via the direct (ö-ö) method using popular thermodynamic models. Such models included the Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) equations of state; with the Mathias Copeman (MC) alpha function, in conjunction with the Huron Vidal (HV) and Wong Sandler (WS) mixing rules and Non-Random Two Liquid (NRTL) activity coefficient model. In general the SRK model in conjunction with the WS mixing rules correlated the experimental data the best.