The commercial application of copper bioleaching, an environmentally-friendly approach for low-grade and secondary mineral resources recycling, has increased worldwide since the 2000s. As the world’s second-largest economic entity and the largest developing country, China has the largest demand for metal resources, significantly advancing the theory and industrial technology of copper bioleaching. This paper reviews the exploration and application of copper bioleaching in China. Two typical bioleaching applications and technological processes, bioheap leaching at the Zijinshan Copper Mine and bioheap leaching at the Dexing Copper Mine, are introduced. The considerable research completed by researchers is summarized, especially focusing on the isolation and identification of leaching bacteria, the bioleaching mechanism and interface reactions, multistage percolation behavior, bioleaching system reconstruction, the multiphysics coupled model, and enhanced copper bioleaching from waste printed circuit boards (WPCBs). Based on this investigation in China, key trends and prospects in copper bioleaching—such as efficiency improvement, environmental protection, and improved technology applications—are proposed.