The authors have investigated effects of thermal oxidation on deep levels in the whole energy range of the band gap of 4H–SiC by deep level transient spectroscopy. The deep levels are generated by ion implantation. The dominant defects in n-type samples after ion implantation and high-temperature annealing at 1700 °C are IN3 (Z1/2: EC-0.63 eV) and IN9 (EH6/7: EC-1.5 eV) in low-dose-implanted samples, and IN8 (EC-1.2 eV) in high-dose-implanted samples. These defects can remarkably be reduced by thermal oxidation at 1150 °C. In p-type samples, however, IP8 (HK4: EV+1.4 eV) survives and additional defects such as IP4 (HK0: EV+0.72 eV) appear after thermal oxidation in low-dose-implanted samples. In high-dose-implanted p-type samples, three dominant levels, IP5 (HK2: EV+0.85 eV), IP6 (EV+1.0 eV), and IP7 (HK3: EV+1.3 eV), are remarkably reduced by oxidation at 1150 °C. The dominant defect IP4 observed in p-type 4H–SiC after thermal oxidation can be reduced by subsequent annealing in Ar at 1400 °C. These phenomena are explained by a model that excess interstitials are generated at the oxidizing interface, which diffuse into the bulk region.