Arsenic is extremely abundant in the Earth’s crust and is one of the most common environmental pollutants in nature. In the natural water environment and surface soil, arsenic exists mainly in the form of trivalent arsenite (As(III)) and pentavalent arsenate (As(V)) ions, and its toxicity can be a serious threat to human health. In order to manage the increasingly serious arsenic pollution in the living environment and maintain a healthy and beautiful ecosystem for human beings, it is urgent to conduct research on an efficient sensing method suitable for the detection of As(III) ions. Electrochemical sensing has the advantages of simple instrumentation, high sensitivity, good selectivity, portability, and the ability to be analyzed on site. This paper reviews various electrode systems developed in recent years based on nanomaterials such as noble metals, bimetals, other metals and their compounds, carbon nano, and biomolecules, with a focus on electrodes modified with noble metal and metal compound nanomaterials, and evaluates their performance for the detection of arsenic. They have great potential for achieving the rapid detection of arsenic due to their excellent sensitivity and strong interference immunity. In addition, this paper discusses the relatively rare application of silicon and its compounds as well as novel polymers in achieving arsenic detection, which provides new ideas for investigating novel nanomaterial sensing. We hope that this review will further advance the research progress of high-performance arsenic sensors based on novel nanomaterials.