Various (AlCrMoTaTi)-Six-N coatings were prepared on Si substrates through a reactive magnetron sputtering system to methodically investigate the effects of Si contents and free Si on oxidation behavior. The as-deposited Si-containing coating presented a relatively dense and compact structure compared with the Si-free coating. An oxide layer was formed on the coating surface and continued to thicken when the coatings were exposed to ambient air at elevated temperatures. At 1073 K, a two-layer structure, which consists of an amorphous Al2O3 layer with traces of other target elements followed by a rutile TiO2 + oxide of the target element mixed zone, was developed in the oxide layer. Oxidation resistance was gradually enhanced with the continued increase in Si concentration in the coatings. At 1173 K, the coatings with Si content of as low as 7.51 at.% exhibited a single order of magnitude lower oxidation rate than that of the Si-free coating. Nanohardness measurement of the coatings further confirmed the oxidation behavior. The significantly enhanced oxidation resistance may be attributed to the presence of Al and Si in the coatings.