The growth mechanism and high temperature oxidation behavior of Si-modified aluminide coatings prepared on a Ni-base single crystal superalloy DD98M using vacuum plasma irradiation were investigated. The growth of the coatings under plasma irradiation was much faster than thermal diffusion-controlled process. The coatings comprised an aluminide outer zone, where Si existed as solid-solute, and an inter-diffusion zone where silicide particles precipitated in aluminide matrix. The crystalline structures of the aluminides were found dependent on the irradiation power. β-NiAl was formed at higher irradiation power while δ-Ni2Al3 was formed at lower irradiation power. The β-NiAl coatings had higher oxidation resistance than the δ-Ni2Al3 ones usually, with an exception of one β coating which was prepared at the highest substrate bias which underwent severe internal oxidation. The presence of numerous voids in the oxide scale of Ni2Al3 may be related to the large number of Kirkendall voids present in the as-prepared coating.