Worldwide experience with Rankine cycle prime movers demonstrates that organic fluids have the potential of meeting future needs of high temperature heat pumps. Many promising candidate fluids exhibit a complex molecular structure, which imparts a peculiar character to the thermodynamics of the heat pump cycle. Since reliable tables of thermodynamic properties are unavailable for most of the fluids of potential interest, a general method was worked out which requires a small amount of data to evaluate the energy performance of different fluid classes. Cycle quality, defined as the ratio of actual to ideal COP*, is recognized to be a function of the following main parameters: complexity of the fluid molecular structure, reduced temperature at which evaporation is performed; fractional temperature lift, DELTA T/T//C. For fluids having rather complex molecules both technical feasibility (owing to condensation during compression) and energy performance are unsatisfactory unless regenerative precooling of the liquid prior to expansion is applied.