Aluminum-containing silicon oxycarbide (SiAlOC) glasses have been obtained through pyrolysis in argon atmosphere at 1000°C of a polymethyl(phenyl)siloxane resin and aluminum tri-sec-butoxide-derived siloxane networks. To investigate their high-temperature behaviors in air environment, these glasses were further annealed at 1000, 1200, 1400, 1600, and 1700°C. It was found that the redistribution reactions between Si–O and Si–C bonds initiated at 1000°C and almost finished at 1200°C; oxidation of the SiAlOC glasses occurred at temperature above 1000°C; and the crystallization of mullite took place at 1400°C due to the inclusion of Al ion into the silica network to form Si–O–Al linkages.