Fe ions were implanted into α-Al 2 O 3 single crystals (sapphire) at energy of 50keV and annealed in an oxidizing environment. Transmission electron microscopy (TEM) investigation indicated that Fe ions in the near surface region precipitated as α-Fe 2 O 3 islands and spinel islands on the specimen surface, at the same time, Fe ions in the region away from the surface precipitated as α-Fe particles in the interior region of specimen. Two orientation relationships (ORs) between the spinel islands and sapphire substrate were discovered as follows: (111) spinel ∥(0001) sapphire , [1 1 2¯]spinel∥[1 1 2¯ 0]sapphire and (1 1 2¯)spinel∥(0 0 0 1)sapphire, [1 1 1]spinel∥[1 1 2¯ 0]sapphire. The first OR was frequently observed in the spinel/sapphire system, however, the second OR has never been reported before. The interfaces between the spinel islands and sapphire substrate are a type-3 incoherent interface (i.e. low-index OR in at least one direction with an ill-matched low-index habit planes). The formation of spinel islands on the specimen surface can be attributed to the oxidizing atmosphere and the low accelerating voltage for ion implantation.