The organic Rankine cycle (ORC) has received a lot of attention in recent years due to its wide application in energy recovery and the use of low‐temperature energy sources. In this article, the energy, exergy, and economic analyses of a high‐temperature ORC (HTORC) in combined heat and power production mode have been performed. In this system, the heating water at 90°C for domestic or industrial purposes is provided in the HTORC condenser. Two working fluids, hexamethyldisiloxane (MM) and siloxane mixture (MDM), have been evaluated and compared in HTORC. The system has been modeled in engineering equation solver software and key parameters such as energy efficiency and exergy of the system, output power, heat‐to‐power ratio, and levelized cost of electricity (LCOE) have been calculated. The energy and exergy efficiency of the system for the two working fluids MM and MDM are equal to 40.8%, 45.6%, 22.45%, and 19.3%, respectively. From the point of view of energy and exergy, the working fluid MM performs better. The LCOE of the system with MM working fluid is equal to 0.5946 US$/kWh, which is slightly higher than MDM working fluid (0.5702 US$/kWh).