The rescue operations’ environment can impair firefighters’ performance and increase the risk of injuries, e.g., burns and hyperthermia. The bulk and carried weight of heavy protection contributes to lower physical performance, higher metabolic load and internal body heat production. For recommending optimal protection for the tasks and incident scenarios, knowledge of clothing thermal properties is needed. However, detailed data on firefighter protective clothing systems are not available. The aim of the study was to provide scientific background and a dataset that would allow for validation of thermo-physiological models for task-specific conditions of rescue work. Thermal insulation of 37 single items and their variations and 25 realistic protective clothing ensembles were measured on a thermal manikin. Twelve (12) ensembles that evenly covered the whole insulation range were selected for evaporative resistance testing. The equations for summing up individual item’s insulation to ensemble insulation and calculating clothing area factor were derived from the dataset. The database of a firefighter clothing system was created. In addition, the local and regional thermal properties of the clothing ensembles were provided for use in future validation of advanced thermo-physiological models for rescue worker exposure predictions and for designing decision aid tools.