ORC represents an effective challenge in the waste heat recovery from ICEs. In spite of technological aspects, its thermodynamic design still deserves attention. Mixtures of pure fluids show interesting properties able to improve exergetic efficiency of the Rankine cycle, thanks to the positive slope of the phase changing. They can reduce also ODP and GWP, helping the replacement trends of working fluids. The paper optimizes cycle exergetic efficiency considering mixtures of pure fluids. The use of hydrocarbons in mixtures is particularly suitable and when used in limited fractions with other organic fluids they loses the limits related to the flammability. R245fa is a fluid that obtains a large net power increase when used in mixtures with hydrocarbons, compared to pure fluid an optimized R245fa/benzene mixture, for instance, attains an 11% net power increase. (C) 2016 Published by Elsevier Ltd.