Overexposure to ultraviolet radiation (UVR) from the sun is associated with deleterious health effects including, but not limited to, increased risk of skin cancers. Military personnel and those who participate in outdoor exercise or sports represent two potential populations at elevated risk of negative health consequences of UVR exposure due to large amounts of time spent outdoors, often in harsh UVR environments. Despite exposure to high and/or frequent doses of UVR in recreational and tactical athletes, adequate sun-protection practices are often disregarded or not well understood by many within these at-risk populations, resulting in heightened risk of negative UVR effects. The focus of this review is to examine the available literature regarding UVR exposure, risk of adverse health effects of UVR exposure, and sun protection practices in outdoor exercisers, athletes, and military personnel.