Background: A set of four case-control (n = 109), randomized-controlled (n = 7), cross-sectional (n = 78), and intervention (n = 47) studies was conducted across three countries to investigate the effects of sun exposure on worker physiology and cognition. Methods: Physiological, subjective, and cognitive performance data were collected from people working in ambient conditions characterized by the same thermal stress but different solar radiation levels. Results: People working under the sun were more likely to experience dizziness, weakness, and other symptoms of heat strain. These clinical impacts of sun exposure were not accompanied by changes in core body temperature but, instead, were linked with changes in skin temperature. Other physiological responses (heart rate, skin blood flow, and sweat rate) were also increased during sun exposure, while attention and vigilance were reduced by 45% and 67%, respectively, compared to exposure to a similar thermal stress without sunlight. Light-colored clothes reduced workers’ skin temperature by 12%–13% compared to darker-colored clothes. Conclusions: Working under the sun worsens the physiological heat strain experienced and compromises cognitive function, even when the level of heat stress is thought to be the same as being in the shade. Wearing light-colored clothes can limit the physiological heat strain experienced by the body.