Abstract The present work concerns the thermochemical and vapor pressure behavior of the pyrene + 9,10-dibromoanthracene system. The phase diagram of the system has been studied using the thaw melt method and the results show the formation of non-eutectic multiphase mixtures. The temperatures of crystallization, and enthalpies of fusion and crystallization of the system were determined by differential scanning calorimetry. The system behavior can be divided into 5 regions. The X-ray diffraction results also indicated the existence of multiple phase characteristics. The solid–vapor equilibrium studies showed that for mixtures with high mole fractions of pyrene, two different preferred states exist that determines the vapor pressure. For those mixtures with moderate and low mole fractions of pyrene, only one preferred state exists that determines vapor pressure behavior. It was also demonstrated that the vapor pressure of the mixtures is independent of the mixture preparation technique.