There has been increased interest to develop protective fabrics and clothing for protecting the wearer from hazards such as chemical, biological, heat, UV, pollutants etc. Protective fabrics have been conventionally developed using a wide variety of techniques. However, these conventional protective fabrics lack breathability. For example, conventional protective fabrics offer good protection against water but have limited ability in removing the water vapor and moisture. Fibers and membranes fabricated using electrospinning have demonstrated tremendous potential to develop protective fabrics and clothing. These fabrics based on electrospun fibers and membranes have the potential to provide thermal comfort to the wearer and protect the wearer from wide variety of environmental hazards. This review highlights the emerging applications of electrospinning for developing such breathable and protective fabrics.