Heat-treated aluminum-silicon (Al-Si)-based alloys have dominated the cast lightweight alloy industry for several decades. However, in the last decade, Al-Ce-based alloys have shown promise in replacing Al-Si alloys due to their ability to remove the need for costly heat treatments. Since the properties of Al-Ce alloys depend on the as-cast microstructure, it is important to characterize the solidification kinetics of these alloys. Therefore, this study focused on characterizing the solidification of a near eutectic Al-Ce alloy with additions of Ni and Mn. The alloy was cast in a wedge mold configuration, resulting in cooling rates between 0.18 and 14.27 °C/s. SEM coupled with EDS and DSC techniques characterized the evolution rate of solid phases. The SEM/EDS data revealed that an Al10CeMn2 phase is present at higher cooling rates. At lower cooling rates, near the center of the casting, a proeutectic Al23Ce4Ni6 phase was more present. It was observed that up to 2.6 at. % of Mn was dissolved in this proeutectic Al23Ce4Ni6 phase, thereby removing a large portion of the available Mn for forming the Al10CeMn2 phase. DSC analysis showed differences in the samples' liquidus temperatures which is indicative of compositional variations. Inductively coupled plasma atomic emission spectroscopy (ICP-OES) and Scheil solidification simulations correlated the compositional differences to phase formation, which agreed with the SEM and DSC results. This experimentation provides insight into novel Al-Ce-Ni-Mn alloys and where their potential lies in industrial applications.