The 450 °C and 600 °C isothermal sections of the Zn–Fe–Ce system were investigated using equilibrated alloys and diffusion couples. The samples were analyzed by Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectrometer analysis and X-ray power diffraction. 15 and 13 three-phase regions were identified to exist at 450 °C and 600 °C, respectively. No ternary compound was found. Ce can not dissolve into all the Zn–Fe binary compounds and the solubilities of Fe in all the Zn–Ce binary phases were limited. All the Zn–Fe compounds can equilibrate with CeZn11 and all the Ce–Zn compounds (except CeZn) can equilibrate with α-Fe. Furthermore, thermodynamic extrapolation of the Zn–Fe–Ce system was carried out and showed good agreement well with detected phase relationships.