Abstract: Gasoline motor vehicles are still the main component of civil motor vehicles, and the pollution of motor vehicle exhaust emissions caused by gasoline quality problems has caused widespread concern. The development of the gasoline octane number certified reference materials (CRMs) plays an essential role in strengthening the quality supervision of gasoline, promoting the prevention and control of atmospheric pollution, and ensuring people's health. With the renewal of the National Standard of Gasoline for Motor Vehicles, the existing gasoline octane number CRMs have been developed to meet people's demand for an improvement of gasoline quality. Based on a comprehensive summary of gasoline grades and knock resistance technical standards, the components, additives and other ingredients that affect the octane number of gasoline and their environmental impact are described, aiming at analyzing the status quo, trend and future direction of the certified reference materials.