Perovskite solar cells have been rapidly developed in recent years. As of 2022, solar cells based on perovskites have achieved a photoconversion efficiency of 25.7%, showing great potential in the field of photovoltaic devices. Despite their high conversion efficiency, the thermal and humidity stability of perovskite solar cells are still considered major barriers to their development. Metal ion doping has proven to be one of the most effective ways to improve the optoelectrical performance and stability of perovskite solar cells. Among the ions introduced, transition metals have been favored by researchers because of their unique properties such as multivalency. In this paper, the latest advancements of doped perovskite photovoltaic devices with transition metal ions are briefly reviewed, and the methods and strategies of doping against the electron transport layer, perovskite active layer, hole transport layer, and metal electrode layer are summarized. The law and mechanism of such methods used to optimize the structure, photoelectric performance, and stability of perovskite photovoltaic devices are discussed.