Small cogeneration (CHP) systems may lead to a significant reduction of primary energy consumption and harmful emissions. Low temperature Rankine cycles, that can be assisted by solar energy, are a possible solution for producing combined electricity and useful heat. These cycles usually use an organic working fluid. This study presents an analysis of the energetic, design and operational features, that have to be taken into account when choosing an adequate working fluid for these Organic Rankine Cycles (ORC). When using renewable energies as a heat source, like solar or geothermal, the cycles may operate at temperatures between 120°C and 230°C. A system producing 5 kW of electricity was considered as a basis of comparison. Several fluids were analysed: n-dodecane, water, toluene, cyclohexane, n-pentane, HFE7100, R123, isobutane and R245fa. The organic dry fluids, with a positive slope of the saturated vapor curve in a T-s diagram, are in principle desirable for low temperature applications, simplifying turbine design. The degree to which the fluids are drying, is generally related to their molecular weight or molecular complexity. Practical issues, like thermal stability, toxicity, flammability and cost are considered. The thermodynamic cycle efficiency is also important. The saturated vapor specific volume gives an indication of condenser size, which is related to system initial cost. A super-atmospheric (>100 kPa) saturation pressure eliminates infiltration gases, which is important for operational reasons, because infiltration reduces system efficiency. The degree of superheating was optimized for maximum cycle efficiency, with a quadratic approximation method. This optimization makes it possible to decide if it is better to have saturated vapor or superheated vapor at turbine inlet, for a fixed turbine inlet temperature. For a heat source temperature of 120°C, only toluene and isobutane present a small advantage in superheating. It is difficult to find the best fluid, which has simultaneously: high cycle efficiency, low vapor specific volume at turbine outlet, super-atmospheric saturation pressure, good thermal stability, small environmental impact, small toxicity and no flame propagation. From the point of view of cycle efficiency, n-dodecane presents the best performance. However, this fluid presents the highest saturated vapor specific volume (resulting in a larger condenser) and the smallest condenser saturation pressure (resulting in infiltration of gases). The best candidates for the cycle regarding all the aspects are: toluene, cyclohexane and n-pentane. Comparing the three fluids, toluene presents the highest efficiency, the highest impact in environment and the biggest vapor specific volume. N-pentane presents the smallest cycle efficiency and smallest vapor specific volume, but is the unique fluid with super-atmospheric saturation pressure. Cyclohexane is the fluid with lowest impact in environment.

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