Solidification of Al–Ce alloys under ultrasonic vibrations (Sonoprocessing) has a significant effect on the refining of Al11Ce3 intermetallic, which plays a key role in controlling the properties of this group of high-performance characteristics. In the current research, a group of as-received Al-10 wt% Ce alloys that were sonoprocessed under different temperatures was characterized. The influence of Al11Ce3 intermetallic size and distribution on the electrochemical properties of these alloys was investigated. Polarization tests in 3.5% NaCl solution were carried out and the recorded Tafel and impedance curves were studied. The corrosion test results were related to the microstructure characteristics as affected by sonoprocessing. Investigation of the as-received samples showed that ultrasonic vibrations broke the long lath-shaped particles of Al11Ce3 and obviously decreased their size and increased their surface area fraction. Sonoprocessing at the optimum temperature, 655 °C, reduced the Al11Ce3 particles size by 90% and enhanced their distribution in the matrix. This in its turn resulted in significant effects on their electrochemical behavior. Polarization tests showed that the corrosion rate of the un-sonoprocessed specimen decreased from ~ 0.00068 to 0.00006 mm/year after processing at the optimum condition (655 °C), and the polarization resistance increased from ~ 71 to 343 kΩ. By increasing the temperature of ultrasonic treatment beyond 655 °C, and the corresponding coarsening of the intermetallic particles, the corrosion rate slowly increased again, and concurrently, the polarization resistance decreased. The size and distribution of the intermetallic particles also influenced the formation of the corrosion pits, where the optimum sample showed shallow pits compared to those observed in the unprocessed specimen. This emphasizes the role of sonoprocessing in controlling the microstructure features and hence the electrochemical properties of Al-10 wt% Ce alloys.