AlNiCo alloy has gained popularity again in recent years due to its good corrosion resistance, affordability, and superior performance at high temperature. However, the lower magnetic properties of AlNiCo limit its wide variety of applications. Directional solidification process is a key process that affects the properties of AlNiCo alloy. During the solidification process, grains with various structures are formed due to the difference of cooling rate at different positions of the ingot. As the cooling rate slows down, the average grain size gradually increases, and orientation degree of the grains becomes better, resulting in the increase of coercivity (Hc) and remanence (Br). Therefore, the top sample has the best Hc and Br, the bottom is the worst, and the middle is between the two. It is found that when the average grain size increases, the percentage of transverse grain boundaries and high angle grain boundaries (HAGBs) decrease, the truncated α1 phase decreases, and the Hc rises, whereas the magnetic moment along the easy-axis direction is not affected by the external magnetic field when the grain orientation coincides, and the Br value increases, and the Br value increases. Large and highly oriented grains are associated with excellent performance, providing a new method to enhancing magnetic properties by regulating the grain structure.