In this paper, the dispersive orientated-precipitation of AlP on γ-Al₂O₃ film and its effect on the primary Si gathering behavior in the near-eutectic Al–Si alloy surface layer was investigated. Experimental results show that (111) orientated AlP can nucleate on the γ-Al₂O₃ film, which is attributed to the high tendency for P to be adsorbed on γ-Al₂O₃ and the good lattice matching relationship between AlP and γ-Al₂O₃. It was also found that the pre-precipitated AlP particles on the γ-Al₂O₃ film could induce Si atoms to precipitate into numerous primary Si particles, leading to an extraordinary high volume fraction of primary Si in the near-eutectic Al–Si alloy surface layer. What is more, the X-ray diffraction experiment shows that the intensity of the Si (111) peak increases significantly and other Si peaks decrease to a very low level, which means that the primary Si particles inherited the (111) orientation characteristic from the orientated AlP grains.