Peripheral nerve damage can lead to loss of function or even complete disability, which brings about a huge burden on both the patient and society. Regulating nerve cell behavior and promoting nerve injury repair by bionic construction of a biological electric field to simulate natural nerve electrophysiological characteristics have attracted great attention, and many studies have shown that electroactive materials have a good repair effect on peripheral nerves. Here, we summarize the electroactive materials commonly used in peripheral nerve repair and their characteristics, especially for the design and application of a biodegradable non-invasive spontaneous electrical system. Besides, based on the fact that electroactive materials can provide electrical conductivity or a power generation performance, the specific role of electroactive materials in peripheral nerve repair was summed up from the following three aspects: cell behavior regulation, signaling pathway regulation and immune microenvironment regulation. This review provides a summary of the current research on the use of electroactive materials in peripheral nerve repair, which may help provide a more effective strategy for peripheral nerve injury (PNI) and allow more patients to benefit from artificial nerve catheter treatment.