The oxidation behavior of Zr2[Al(Si)]4C5 and Zr3[Al(Si)]4C6 in air has been investigated. The oxidation kinetics of bulk Zr2[Al(Si)]4C5 and Zr3[Al(Si)]4C6 at 900–1300 °C generally follow a parabolic law at a very short initial stage and then a linear law for a long period with the activation energy of 237.9 and 226.8 kJ/mol, respectively. The oxide scales have a duplex structure, consisting of mainly an outer porous layer of ZrO2, Al2O3, and aluminosilicate/mullite, and a thin inner compact layer of these oxides plus remaining carbon. The oxidation resistance of Zr2[Al(Si)]4C5 and Zr3[Al(Si)]4C6 has been improved compared with Zr2Al3C4, and is much better than ZrC due to larger fraction of protective oxidation products, Al2O3 and aluminosilicate/mullite.