This work describes vapour pressure measurements of a water/synthetic naphtha mixture using a dynamic CREC‐VL‐Cell, designed to obtain reliable vapour measurements (). The CREC‐VL‐Cell is used to measure vapour pressures for immiscible or partially miscible liquids, given its high multiphase mixing capability. Runs in the CREC‐VL‐Cell involve a dynamic method, operating with a set heating ramp, with continuous tracking of both saturation vapour pressure and temperature within the cell. This system allows for the establishment equilibrium vapour pressures, in a recommended 50–120°C range, emulating the conditions of the naphtha recovery in oil sand processes. Results obtained in the CREC‐VL‐Cell at 1080 rpm are validated using data from Aspen‐Hysys with a Peng‐Robinson fluid package for pure octane and water. On the other hand, using a 2.5 wt.% and 4 wt.% synthetic naphtha in 97.5 wt.% water blend, experimental data shows partial agreement with the Aspen‐Hysys Peng‐Robinson fluid package predictions, demonstrating the value of the experimental vapour‐liquid–liquid (VLL) data obtained in the CREC‐VL‐Cell.