Intense physical activity and high ambient temperature cause construction workers to be exposed to an increased risk of overheating, especially in the summer season. Personal cooling systems have great potential to support workers’ thermoregulation and reduce this risk. In particular, solutions based on the thermoelectric effect can provide high cooling effectiveness and ergonomics at the same time. In this paper, a newly developed active clothing solution with flexible thermoelectric modules intended for outdoor activities is presented. The active clothing was subjected to utility tests on a treadmill under laboratory conditions with the participation of potential end users. A comparison of results from cooled and uncooled places indicated a reduction in local skin temperature of as much as 2.7 °C. Moreover, a gradual decrease in temperature in the uncooled place during the experiment was observed. Based on the positive results from this evaluation, the personal cooling system was integrated into active clothing within the ASSIST-IoT NGIoT reference architecture. This allows contextual and personalized adjustment of the cooling power to be provided using AI techniques and, additionally, by using data from a weather station and a smartwatch. Training procedures and models for the AI system are proposed, with special attention paid to the privacy aspect.