Arsenic (As) and antimony (Sb) contamination poses significant health risks, manifesting in a spectrum of ailments such as cardiovascular, respiratory, and skin diseases and the development of cancer. When toxic elements enter the body through different exposure routes, they can cause serious health issues. This highlights the critical need to reduce their presence in the environment to protect public health. When detecting As and Sb in different samples, researchers prefer to use whole-cell and optical biosensors rather than electrochemical (EC) biosensors for reliable detection. Utilizing EC biosensors can significantly enhance the detection thresholds and accuracy of monitoring environmental changes. It is particularly well suited for applications requiring high sensitivity, rapid detection, portability, and cost-effectiveness. For fast onsite environmental monitoring, its portability and quick reaction times are essential. The augmentation of EC biosensors via AI integration has the potential to transform pollution detection, healthcare diagnostics, and food safety monitoring, in addition to enhancing their sensitivity and accessibility. This review highlights the potential benefits of EC biosensors and their diverse applications in environmental monitoring. It critically evaluates strategies aimed at enhancing the efficiency of environmental monitoring processes.