AbstractThe thermal stability analysis of perfluorohexane (C6F14)is presented in this paper as a preliminary evaluation of the potential application of the binary mixture CO2 – C6F14 as innovative working fluid for transcritical-CO2 power cycles. After presentinga description of the experimental apparatus, saturation pressure models are compared and calibrated over measurementsof the virgin fluid (C6F14). Moreover, the methodologyapplied to attest the occurrence of a thermal decomposition is described. Finally, the paper presents a thermodynamic analysis of themeasurements obtained from the partially decomposed system,performed to investigate the nature ofthe partial thermal decomposition process.