This review focuses on advanced materials already used and suitable for application in (future) lunar extravehicular activity space suits. A historical and current literature/market survey is presented. Different functional layers of an astronaut garment are defined with emphasis on the external layers subjected to abrasive action of lunar regolith and degradation via exposure to space radiation/vacuum environment. Requirements are defined that would need to be fulfilled by these layers and suitable materials candidates are reviewed based on their key properties, including mechanical durability. Smart materials, combining additional functionalities, such as garment health monitoring, are also considered. The lead topic is the subject of an ongoing ESA‐funded research activity.