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This study investigates the thermal insulation and moisture management of three types of mountaneering boots and simulated hiking activities under controlled environmental conditions with two elite athletes. Temperature and humidity were determined with six wireless probes placed on the most exposed parts of the foot (hallux, middle toe, little toe, dorsum, ankle and sole). Thermal images were taken to record the thermal insulation of each sample. Methodologically, the study aims to simulate every movement and activity of alpinism in order to realistically evaluate the conditions of use of this kind of footwear (also taking into account the lacing pressure exerted on the foot). Based on the results obtained, in a further step it will be possible to define the best solution in terms of combination of materials by creating a comfort scale for hiking boots.