Waste PCBs (Printed Circuit Boards) from LCDs (Liquid Crystal Displays) contain valuable raw materials, Sn, Cu, and other noble metals. Among these, high purity tin was obtained by electro-winning after appropriate acid leaching of tin. For this, leaching and electro-winning process parameters were optimized for solution stability, dissolution and electrolytic efficiency. Two aqueous procedures were developed and tested for electro-winning at mass-production capable basis: (1) HCl leaching after preliminary HNO₃ dissolution was quite effective in leaching high proportion of Sn as analyzed by ICP (Inductively Coupled Plasma) method. (2) Direct one-step leaching in H₂SiF₆ + H₂SO₄ + H₂O₂ was also tested and the solution was finally selected as electrolytes in electro-winning due to massproduction capability. The most efficient recovery of tin was observed after 7h electro-winning in aqueous H₂SiF₅ + H₂SO₄ + H₂O₂ maintained at 40: 96%-pure tin was obtained with 93.2% recovery rate.