In this study, the nucleation and growth mechanisms of Al11Ce3 intermetallic compounds (IMCs) in a hypereutectic Al–Ce alloy during solidification were investigated through synchrotron radiation X-ray real-time imaging. The results showed that Al11Ce3 IMCs nucleate and grow from the melt as the primary phase at the initial stage of solidification. Growth preferred orientations were observed in two opposite directions, resulting in an I-shaped growth pattern. Based on the minimum energy criterion, the morphology of Al11Ce3 IMCs displayed either hollow cubic tubes or grooves. The nucleation and growth rates of Al11Ce3 IMCs gradually decreased over time, owing to the variations in the Ce concentration in the melt and the undercooling. The nucleation and growth characteristics of Al11Ce3 IMCs can provide the theoretical basis for optimization on the performance of Al–Ce alloys.