Auxetic behavior is a promising new area for use in defense applications. In comparison to a conventional material, an auxetic material has superior properties because of having a negative Poisson’s ratio; it gets broadened when stretched or becomes smaller when compressed. Furthermore, auxetic materials have enhanced properties such as shear resistance, indentation resistance, fracture toughness, energy absorption, and so on. These improved properties make auxetic materials very appealing and have the potential to revolutionize their applications in aerospace, sports, automotive, construction, biomedical engineering, smart sensors, packaging, cushioning, air filtration, shock absorption and sound insulation, and defense personal protective equipment. This article examines the most recent scientific advances in auxetic materials and structures, such as auxetic textiles (fibers, yarns, and fabrics), auxetic textile-reinforced composites, and auxetic foams, as well as their exceptional auxetic behavior and various approaches to achieving them. Although many potential applications have been proposed, actual applications of auxetic materials in defense are still limited. This is an in-depth review article, and its main goal is to serve as a foundation for future studies concerning the topic.