The phase behaviour of heavy oil mixtures was studied using an X-ray imaging system. Batch phase experiments were performed at temperatures and pressures up to 725 K and 7 MPa. Complex phase behaviour such as liquid-liquid-vapour and solid-liquid-liquid-vapour were observed and preliminary experimental phase diagrams were constructed. This observed complex phase behaviour is consistent with thermodynamic theory and such phase behaviour can be modelled using the Peng-Robinson equation of state and the tangent plane criterion. These latter points are illustrated through the phase diagram for a model reservoir fluid (ethane + propane + n-butane + phenanthrene) which exhibits solid-liquid-liquid-vapour phase behaviour. Example predicted and experimental phase diagrams are presented for this model system.