A concentrated calcium chloride(CaCl2)-based electrodeposition bath was investigated for use in low-toxicity tin-silver(Sn-Ag)alloy plating processes and for facile recovery of metal components from used plating bath(s). Flat electrodeposition was achieved using a Sn-Ag alloy electrodeposition bath: 5 mM AgCl+195 mM SnCl2+12 mM HCl in CaCl2・10H2O. Moreover, a simple pH adjustment and subsequent filtration removed 99% of the silver as precipitate, leaving tin in the solution. Results show that concentrated CaCl2 aqueous solutions might be used as a Sn-Ag alloy plating bath, thereby facilitating the selective recovery of metal components.