Methanesulfonic acid (MSA) is used to recover silver (Ag) from solar cells by adding an oxidizing agent. It is possible to regenerate by substituting of H+ for Ag+, and thus it can be reused for additional reactions. However, MSA is highly hygroscopic, and as an oxidizing agent can easily decompose in the acidic environment during Ag extraction, leading to dilution due to the formation of H2O. This H2O in the MSA solution hinders the Ag extraction. In this study, we present a fractional distillation process for restoring the reactivity of reused MSA solutions by reducing the H2O content. Our results showed that the reactivity of the separated MSA was restored and Ag could be recovered from the solar cell.