The work aim to review the basic principles and influencing factors of microbial electrosynthesis (MES) for the production of polyhydroxyalkanoates (PHAs) and the challenges of their application in the packaging industry, with a view to optimizing the production process, achieving efficient and low-cost synthesis of PHAs, and broadening the synthesis technology of green packaging materials. Based on the latest research progress at home and abroad in recent years, shortcomings of the existing methods for synthesizing PHAs were summarized, MES synthesis methods and principles were introduced, influencing factors of PHAs synthesis by the MES system were described, and challenges faced by the MES system in the synthesis of green packaging materials such as PHAs were discussed. In conclusion, the MES system has great research potential in synthesizing PHAs. The key research directions in the future are the development of highly efficient electroactive microorganisms, the optimization of electro-synthesis conditions and the structure of the MES system to improve the yield of PHAs, and the broadening of the application of the MES system in synthesizing biodegradable packaging materials.