This paper review presents a comparison between conventional leaching and advanced photochemical leaching processes and their potential for use in chalcopyrite leaching. Likewise, it presents an analysis of the differences between the advanced leaching processes, photoleaching and radical-leaching, indicating that the photochemical mechanisms (photooxidation/photoreduction and generation of radical oxygen species (ROS) and radical sulfur species (RSS)) would improve the oxidative dissolution of chalcopyrite, taking advantage of the high oxidizing power of free radicals. Initial experimental results of solar-assisted radical-leaching on chalcopyrite are presented, demonstrating that sulfate radicals (SO4−) allow copper to be leached at a rate 4.7 times higher than in the absence of radicals and sunlight. With these results, a radical-leaching process is presented for the first time, with a perspective toward the future development of a new hydrometallurgical route: solar-assisted radical-leaching.