Hypereutectic Al-Si alloys have low thermal expansion coefficients, excellent wear resistance, and high hardness. To replace cast iron with hypereutectic Al-Si alloys, the hypereutectic Al-Si alloys must still have the originally desired mechanical properties. The addition of Fe and Mn to the hypereutectic Al-Si alloys can form Fe-rich phases, which can improve thermal stability. In this paper, the effect of manganese (0 %, 0.99 %, and 1.36 %) on the Fe-rich phases of hypereutectic Al-22Si-2Fe (% w/w) alloys was studied. The results showed that primary Si particles (PSPs), needle-like Fe phases, a coarser fishbone-shaped α-Al15(Fe, Mn)3Si2 phases, and eutectic Si could be refined by cooling slope. With such a CS process, the intermetallic compounds in the alloys with different Mn/Fe ratios were examined with an optical microscope, scanning electron microscope, and X-ray diffraction. Moreover, the blocky α-Al15(Fe, Mn)3Si2 phases were analyzed by transmission electron microscopy. Through the analysis of the SADP, the lattice structures of α-Al15(Fe, Mn)3Si2 phases were identified with tetragonal structure and body centre cubic.