In this study, a biodegradable silk fibroin/poly(lactic-co-glycolic acid)/graphene oxide (SF/PLGA/GO) microfiber mat was successfully fabricated via electrospinning for use in protective fabrics. The morphology of the microfiber mat was characterized by Scanning Electron Microscope (SEM). The thermal and mechanical properties, water contact angle, surface area and pore size of the microfiber mats were characterized. Due to the introduction of graphene which can interact with silk fibroin, the SF/PLGA/GO microfiber mat, compared with the silk fibroin/poly (lactic-co-glycolic acid) (SF/PLGA) microfiber mat, has higher strength, greater Young's modulus and better thermal stability which can meet the requirements of protective fabric. The microfiber mat is biodegradable because its main component is silk fibroin and PLGA. In particular, the microfiber mat has a small pore size range of 4 ∼ 10 nm in diameter, a larger surface area of 2.63 m g and pore volume of 7.09 × 10 cm g. The small pore size of the mat can effectively block the particulate pollutants and pathogenic particles in the air. The larger surface area and pore volume of the mat are effective for breathability. Therefore, the fabricated SF/PLGA/GO microfiber mat has great application potentials for protective fabrics.