The effects of Ca, Al, and Ag on the anti-oxidation of Sn-9Zn-X solders and the interface reactions between the solders and Cu substrate were investigated by Auger electron spectroscopy (AES) and scanning electron microscope (SEM) analysis, respectively. The mechanism of improving the wettability of Sn-g Zn lead-flee solder by adding Ca, Al, and Ag was also revealed. The AES analysis indicated that Al and Ca might enrich on the molten solder surface which resulted in improving the anti-oxidation of Sn-gZn-O. O05Al and Sn-gZn-O. 3C, a alloys. The addition of Ca reduced the apparent activation energy and promoted the interface reaction. With the addition of 0.3 wt. % Ag, some scallop-like intermetallic compounds (IMCs) formed at the interface, according to the energy dispersive spectroscopy (EDS) analysis, these scallop-like IMCs might be the mixture of Ag-Zn and Cu-Sn compounds.