This work paper presents vapour–liquid equilibrium (VLE) data for binary (CO2 + nicotine) and ternary (CO2 + nicotine + solanesol) mixtures, at 313.2 K and 6, 8 and 15 MPa. The (CO2 + nicotine) system exhibits three phases (L1L2V) in equilibrium at 8.37 MPa. It is estimated that this system most likely follows the type-III phase behaviour. In the ternary system, the presence of solanesol in the vapour phase was detected only at the pressure of 15 MPa. At this pressure, partition coefficients and separation factors for solanesol/nicotine were calculated for different initial nicotine/solanesol compositions and a strong influence of composition was found. The results were modelled using the Peng–Robinson equation of state (PR EOS) coupled with the Mathias–Klotz–Prausnitz (MKP) mixing rule (PR–MKP model). Good correlations of the binary data, particularly in the case of the (CO2 + nicotine) mixture, were obtained. However, the model could not correlate the ternary data.