This chapter reviews smart and high performance materials that are currently used in protective textiles or are being investigated by researchers for protective applications. Fibres with high strength, heat resistance, chemical resistance, and electrical conductivity are discussed. Materials with piezoelectric properties for sensing and actuation, phase change materials that absorb and release heat, and shear thickening fluids are briefly covered. Protective films and electrospun nanofibre membranes and their methods of manufacture are described, as are nanofibres derived from natural sources. Applications of carbon nanotubes are reviewed and some discussion is given of why the outstanding properties of individual nanotubes are not yet fully exploited in macroscopic assemblies as pure nanotube fibres or as composites with a polymer resin.