The wireless sensor network energy supply technology for the Internet of things has progressed substantially, but attempts to provide sustainable and environmentally friendly energy for sensor networks remain limited and considerably cumbersome for practical application. Energy harvesting devices based on the magnetoelectric (ME) coupling effect have promising prospects in the field of self‐powered devices due to their advantages of small size, fast response, and low power consumption. Driven by application requirements, the development of composite with a self‐biased magnetoelectric (SME) coupling effect provides effective strategies for the miniaturized and high‐precision design of energy harvesting devices. This review summarizes the work mechanism, research status, characteristics, and structures of SME composites, with emphasis on the application and development of SME devices for vibration and magnetic energy harvesting. The main challenges and future development directions for the design and implementation of energy harvesting devices based on the SME effect are presented.