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The microstructure of an as-cast Mg-Zn-Er alloy was investigated through scanning electron microscopy (SEM) and transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS). The results indicate that two different second phases, one with eutectoid-lamellar morphology and the other with granular shape, distribute in the α-Mg matrix. The coexistence of the face-centered icosahedral quasicrystalline phase (I-phase) and W-phase with the face-centered cubic structure is found in the as-cast alloy. The coexistence of I-phase and W-phasc in the Mg-Zn-Er alloy is because the W-phase is the primary phase and the I-phase forms by peritectic reaction during solidification.