There are various organic compounds that can be utilized in the organic Rankine cycle as working fluids. The selection of a suitable working fluid is complicated due to the large number of options and factors affecting the choice, such as thermodynamic properties, environmental impact, cost, etc. This study evaluates seven different pure organic compounds and twenty-one of their binary zeotropic mixtures as potential working fluids for the organic Rankine cycle powered by a heat source at 200 °C. The pure organic fluids show higher exergy efficiency, higher specific net power output, and lower heat exchange area requirements compared to the binary mixtures. Among the pure fluids, RE347mcc performs the best in terms of exergy efficiency, followed by neopentane, isopentane, and pentane. Cyclopentane exhibits the highest power production capacity per unit mass flow rate of the working fluid. Two mixtures, pentane/Novec 649 and cyclopentane/Novec 649, showed significantly higher exergy efficiency than their individual components, but at significantly lower specific power production capacity. The study presents an interesting trade-off between exergy efficiency and heat exchange area, indicating that a small increase in exergy efficiency can lead to a large decrease in the required heat exchange area. The outcomes of this study can help in selecting suitable working fluids for ORC operation with a heat source at 200 °C.