Valuable and toxic metals including Ag, Pb, Sn and Cu can be recovered from end-of-life Si solar modules. This study presents the recovery of Ag, Pb, Sn and Cu from a simulated leach solution of crystalline-Si modules. 11.4% HNO3 is used as the leach solution. Ag, Pb, Sn and Cu pellets are dissolved in the solution to simulate the metals from front contacts and soldered wires in Si modules. Sn precipitates in the solution as SnO2, which can be separated by filtration or sedimentation. Voltammetry reveals the reduction potentials for Ag and Cu. It is demonstrated that 3-electrode sequential electrowinning can extract Ag and Cu one by one from the solution. The recovery rates of Ag and Cu are 74% and 83%, respectively. Toxic Pb is deposited on the anode as PbO2 during Cu recovery. The purity of the extracted metals is above 99%.