Semiconductor photocatalysis technology is considered to be a promising technique to solve increasingly serious environmental pollution. Metallic bismuth (Bi)‐based photocatalysts have received much attention due to their extensive applications in environmental remediation because metallic Bi can function as a cocatalyst or a direct plasmonic photocatalyst to accelerate the photogenerated charge separation and thus improve their photocatalytic activity. In the last decade, enormous efforts have been made to seek excellent metallic Bi‐based photocatalysts as well as reveal the corresponding photocatalytic reaction mechanism for the degradation of organic pollutants in water. Herein, the unique electronic and optical properties and main synthesis methods of metallic Bi, as well as the detailed strategies and technology routes are timely summarized and discussed to enhance the photocatalytic activity of metallic Bi‐based photocatalysts in water purification. Finally, the future development and challenges of metallic Bi‐based photocatalysts are briefly discussed, summarized, and prospected.