The surface oxidation mechanism of lead-free solder alloys has been investigated with multiple reflow using X-ray photoelectron spectroscopy. It was found that the solder surface of Sn-Ag-Cu-In solder alloy is surrounded by a thin $InO_x$ layer after reflow process; this coating protects the metallic surface from thermal oxidation. Based on this result, we have performed a wetting balance test at various temperatures. The Sn-Ag-Cu-In solder alloy shows characteristics of both thermal oxidation and wetting balance better than those of Sn-Ag-Cu solder alloy. Therefore, Sn-Ag-Cu-In solder alloy is a good candidate to solve the two problems of easy oxidation and low wettability, which are the most critical problems of Pb-free solders.