Electrochemical sensors, as a fast, accurate, and stable type of sensor, process wide applications and promising development prospects in various scenarios such as environmental monitoring, medical diagnosis, and food safety. The generated electrical signals by reactions between electrode materials and targeted analytes enable quantitative or qualitative analysis of the target substances, which always displays more efficient, highly sensitive, and portable compared to the traditional detection methods such as high-performance gas (liquid) chromatography. However, the existence of several core factors (electrode, electrolyte, and signal collection devices) commanded the applicability of electrochemical sensors, practically electrode components. This review summarizes the detection mechanisms and advanced performances of several typical electrode materials and additives used in non-enzyme electrochemical sensors. It also highlights the unique application advantages in detecting nitrite, glucose, heavy metals, and pesticide residues in food safety. The insight provides a sneak peek on suites of electrode materials, including their synthesis process, overall non-enzyme sensor performance, and future perspectives.