Crystalline silicon photovoltaic (PV) cells contain material resources such as silver (Ag), copper (Cu), aluminum (Al), silicon (Si), glass, and resin. Approximately 600 g/t of Ag is contained as a current collector, so-called finger wires, in PV modules; hence, the recovery of Ag from spent PV panels is an important issue. For Ag recovery, it is necessary to separate the resin part before a nitric acid dissolution process to reduce recycling cost. In this study, an electrical wire explosion was applied to the Ag finger wires to achieve high separation selectivity with a small number of discharges. Three kinds of experiments were conducted: (1) electrical explosion, (2) mechanical milling, and (3) a combination method, that is, additional mechanical milling of the remaining cell sheet after the electrical explosion. The particle size distribution, Ag concentration, and Ag recovery ratio were compared for each condition. The PV cell sheet sample was prepared by removing the aluminum frame and cover glass plate from a spent PV panel. Electrodes were placed on Cu busbars, to which 102 Ag finger wires were connected, diagonally across the cell sheet sample. The Ag finger wires between the electrodes were exploded by applying pulsed electrical energy. As a result of the electrical explosion experiment, Ag was recovered as particles smaller than 1.18 mm and the recovery ratio was 36.9%. Only Ag finger wires between the busbars connected to the electrodes were exploded and the Ag that existed outside of the electrodes was hard to recover. The combination method successfully increased the recovery ratio of Ag. The additional mechanical milling process concentrated all of the remaining Ag in the cell sheet after the electrical explosion into the ground size fraction under 4 mm, showing a higher separation efficiency than that of simple mechanical milling because the electrical explosion separated the Ag from the resin.