Health Care Organizations are large consumers of energy resources. This is due to the large number of services they must offer continuously, the strict requirements of temperature and humidity for patients and comfort for all visitors. Facilities for thermal energy production are critical as they guarantee the proper working of care services by producing primary air, eliminating legionella, and providing air conditioning to theatres, emergency areas, ICUs, neonatology departments, etc. Nonetheless, despite the importance of thermal energy production systems, there is no prior literature analysing the best maintenance to be applied to these systems. This study describes an innovative multicriteria model designed with the Measuring Attractiveness by a Categorical Based Evaluation Technique (MACBETH) approach and Markov chains, in choosing the best combination of maintenance policies to guarantee the best quality of care. The model was created with the co-operation of a decision group made up of those in charge of different areas of a Health Care Organization. This gives the current availability of the thermal energy production systems, and the availability that would be achieved by applying other alternatives. In the system that produces hot water for the air conditioning units, the best alternative is found to be corrective and preventive maintenance. In the cold-water production system for air conditioning, the model recommends the use of corrective, preventive and predictive maintenance, monitored by vibration analysis. For the systems producing hot domestic water and hot and cold water for other systems, corrective and preventive maintenance is recommended. In the legionella treatment system, it is best to apply corrective, preventive and periodic predictive maintenance (quarterly by combustion analysis). Finally, the implications for quality of care of changing the maintenance alternatives are considered. This research was carried out on thermal energy production systems currently operational in the University General Hospital of Ciudad Real (Spain). The methodology used in this study, together with the criteria, descriptors, weightings, etc., may serve as a standard for other Health Care Organizations, with the final goal of improving quality of care.