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An orthogonal method was used to evaluate the effects of Ga, AI, Ag, and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solders by wetting balance method. The results show that the optimal loading of Ga, Al, Ag, and Ce was 0.2 wt.%, 0.002 wt.%, 0.25 wt.%, and 0.15 wt.%, respectively, Intermetallic compounds (IMCs) formed at the interface between Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder and Cu substrate were investigated by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analy-sis. The SEM images illustrate that the IMCs can be divided into two portions from the substrate side to the solder side: a planar Cu_5Zn_8 layer and an additional continuous scallop-like AgZn_3 layer. The EDS analysis also shows that Ga segregates in the solder abutting upon the inter-face. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) of the surface components of Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder indicate that Al aggregates at the surface in the form of Al_2O_3 protective film, which prevents the further oxidation of the solder surface. On the other hand, Ce aggregates at the subsurface, which may reduce the surface tension of the solder and improve the wettability in consequence.