The exposure to extreme temperatures in workplaces involves physical hazards for workers. A poorly acclimated worker may have lower performance and vigilance and therefore may be more exposed to accidents and injuries. Due to the incompatibility of the existing standards implemented in some workplaces and the lack of thermoregulation in many types of protective equipment that are commonly fabricated using various types of polymeric materials, thermal stress remains one of the most frequent physical hazards in many work sectors. However, many of these problems can be overcome with the use of smart textile technologies that enable intelligent thermoregulation in personal protective equipment. Being based on conductive and functional polymeric materials, smart textiles can detect many external stimuli and react to them. Interconnected sensors and actuators that interact and react to existing risks can provide the wearer with increased safety, protection, and comfort. Thus, the skills of smart protective equipment can contribute to the reduction of errors and the number and severity of accidents in the workplace and thus promote improved performance, efficiency, and productivity. This review provides an overview and opinions of authors on the current state of knowledge on these types of technologies by reviewing and discussing the state of the art of commercially available systems and the advances made in previous research works.