In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO4), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25mm, 25mL 80% (v/v) ionic liquid, 10mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70°C and 2h. Copper leaching by [bmim]HSO4 can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36kJ/mol.