Endohedral Metallofullerenes (EMFs) have garnered significant attention for their distinctive properties and their prospective integration into cutting-edge photoelectric devices. This review provides a comprehensive overview of the recent progress in the synthesis of EMFs, highlighting a novel “self-driven carbon atom implantation” approach that sheds new light on the underlying mechanisms of EMF formation. The discussion delves into the pivotal challenges of yield optimization and purification processes, addressing the current limitations and the imperative for scalable synthesis and improved stability. Furthermore, the review explores the burgeoning applications of EMFs in the domain of photoelectric energy conversion, with a particular focus on their capacity to augment the efficiency of photovoltaic devices. Their unique electronic structures and tunable energy levels are underscored as key factors that contribute to improved charge separation and enhanced overall performance. In conclusion, the review offers a forward-looking perspective on the interdisciplinary research avenues that are essential for harnessing the full potential of EMFs. It emphasizes the need for collaborative efforts across materials science, chemistry, and nanotechnology to overcome existing hurdles and to integrate EMFs into next-generation energy conversion technologies, thereby paving the way for more efficient and sustainable energy solutions.