To elucidate the segregation behavior of solutes in Al-Si and Al-Cu binary alloys, specimens of several hypo-eutectic Al-Si alloys water-quenched at different stages of solidification or air-cooled from melt to room temperature were prepared and the distributions of Si concentration were analyzed across the primary dendrites. The Si distribution in the dendrites of the specimens water-quenched during primary solidification showed that Si concentration declined from the surface toward the center of the dendrite. In contrast, the specimens water-quenched after eutectic solidification or air-cooled from melt to room temperature showed that Si concentration increased from the surface toward the center of the dendrite. The diffusion distance of Si in the dendrites during the cooling process from the finish of solidification to room temperature was calculated according to Fick's second law and showed good agreement with the measured value. Therefore, the segregation behavior with high Si concentration in the center of the dendrite was attributed to the diffusion of Si from the center to the surface of the dendrite, resulting in the precipitation on the adjacent Si phase during eutectic solidification.