Endohedral metallofullerenes (EMFs) have garnered significant attention for their distinctive properties and potential integration into cutting-edge photoelectric devices. This review provides a comprehensive overview of recent advancements in EMF synthesis, highlighting the novel "self-driven carbon atom implantation" approach that sheds new light on the underlying mechanisms of EMF formation. The discussion delves into pivotal challenges related to yield optimization and purification processes, addressing current limitations and the imperative need for scalable synthesis and improved stability. Furthermore, the review explores the burgeoning applications of EMFs in photoelectric energy conversion, focusing on their capacity to enhance the efficiency of photovoltaic devices. Their unique electronic structures and tunable energy levels are highlighted as key factors contributing to improved charge separation and overall performance. In conclusion, this review offers a forward-looking perspective on interdisciplinary research avenues essential for harnessing the full potential of EMFs. It underscores 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.