An experimental test was conducted to compare R245fa with R245fa/R601a on the organic Rankine cycle performance. The major objective of this paper is to ascertain the highest thermal efficiency and the optimal dimensionless volume ratio using the two working fluids. The experimental system consists of an electrically heated boiler, a vapor generator, a scroll expander, a condenser, a working fluid pump, and so on. For the typical weather conditions of May in Tianjin, the experiment results show that the working fluid charge has an important influence on the organic Rankine cycle performances. The optimal isentropic efficiency of the scroll expander corresponds to the design expansion ratio. Underexpanded and overexpanded processes result in the decline of the isentropic efficiency of the scroll expander, with the former playing a major role. R245fa/R601a improves the heat transfer performance in the vapor generator because of the nonisothermal phase change. The highest thermal efficiency for R245fa and R245fa/R601a is 4.38% and 4.45%, thereby illustrating that R245fa/R601a precedes R245fa. The optimal dimensionless volume ratios for R245fa and R245fa/R601a are 0.38 and 0.41, respectively. The experimental test lays foundation of the 500-kW geothermal plant for demonstration in the next step. Copyright (c) 2014 John Wiley & Sons, Ltd.