The continuous research and development regarding firefighters’ personal protective equipment (PPE) has led to significant improvements in recent decades. Despite the evolution of firefighters’ PPE, every year an undesirable number of firefighters are seriously burned during firefighting operations, with some of them eventually losing their lives. The protection given by firefighters’ PPE can be further increased with the incorporation of smart textiles in the personal protective equipment, namely, wearable electronics (i.e., integrated sensors to monitor diverse parameters: heart rate, oxygen saturation, carbon dioxide detector, and setting real-time communication with a command post) and advanced materials such as phase change materials (PCMs). The evolution of firefighters’ PPE has been followed by an evolution and update in the international and national standards that specify performance requirements for firefighters’ protective clothing for structural and wildland firefighting as well as technical rescue. This study will focus on the analysis of firefighters protective clothing evolution regarding the use and integration of advanced smart materials, namely, phase change materials, taking into consideration the evolution and requirements of international and European standards as well as national legislation for firefighters’ protective clothing.