AZ91‐0.9Ce alloy with a thickness of 8 mm is prepared by die casting. The formation process of main compounds in the alloy, the role of main compounds in fracture process, the main crack source, and crack propagation path of the alloy are studied. Results show that AZ91‐0.9Ce alloy is mainly composed of α‐Mg matrix, Mg17Al12 compound, Al4Ce compound, and a small amount of Al–Mn–Ce ternary compound. Among them, Al4Ce is formed prior to the Mg17Al12 compound. Mg17Al12 is formed by eutectic reaction, and Al–Mn–Ce ternary compound is formed at a later stage of solidification. Mg17Al12 and Al4Ce are the main crack sources of the alloy during the fracture process. Crack locations in the alloy mainly include grain boundaries, phase boundaries, and Mg17Al12 and Al4Ce compounds. The fracture mechanism of the alloy is that with the increase of load cracks occur at Mg17Al12 and Al4Ce compounds and connect with each other through intergranular and a small amount of transgranular to form the main crack. With the load continues to increase, the main crack gradually expands until alloy fracture failure. The continuous network distribution along grain boundaries of the Mg17Al12 compound is an important reason for intergranular fracture.