The microstructures of as-cast and as-solution Mg–12Gd–2Er–1Zn–0.6Zr alloys were investigated by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and selected-area electron diffraction (SAED) in the present investigation. The results show that the primary eutectic phase Mg5(Gd, Er, Zn) and some flocculent features are found in the as-cast alloy; the SAED pattern indicates that these flocculent features are the dense areas of stacking faults. The 14H-LPSO structure precipitates in the temperature range of 673–793 K, and the volume fraction of 14H-LPSO structure increases with the extension of heating time; however, there is no precipitation of 14H-LPSO structure when the temperature reaches up to 803 K. In addition, the Mg5(Gd, Er, Zn) phase dissolves gradually along with the precipitation of 14H-LPSO structure.