Traditional luminescent materials commonly exhibit single‐duration emissions and single‐timed emissions with limited emission peaks. Developing a material with multicolor, variable temporal, and multimodal luminescence is a significant challenge. Self‐reduction phosphors have attracted considerable interest for their distinctive properties and versatile applications. Distinguished by their rigid structure and exceptional purity, offer a safer alternative to conventional reduction methods using hazardous gases H2/CO/N2. However, synthesizing these phosphors with precise control over self‐reduction and defect regulation is complex. Therefore, innovative structures and substrates are essential to address these challenges. This review discusses the latest developments in phosphors doped with ions such as Eu3+, Mn4+, Ce4+, and Yb3+, examining the origins and advancements in self‐reduction. It covers classifications, mechanisms, defects, and applications, with an emphasis on techniques for controlled self‐reduction through structural and charge transfer modifications. This work aims to provide valuable insights to facilitate further research and innovation endeavors.