Pb(⋅Si≡Si3) andE’(⋅Si≡O3) centers in the Si/SiO2structure under gamma‐ray radiation are studied with the electron‐spin‐resonance technique. The Si/SiO2structures of (111), (110), and (100) planes are obtained using three different oxidation methods to control the concentration of the hydrogen‐related impurities. It is first observed that the concentration ofPbcenters is decreased with increasing radiation dosage in samples with lower concentrations of impurities; the concentration dramatically increases in the samples with a higher concentration of impurities. The concentration ofE’centers also increases with accumulated dosage. When the Si/SiO2structure is fabricated under different oxidation temperatures, the saturated concentrations ofPbcenters after irradiation depend upon the oxidation temperature. The concentration ofE’centers increases with oxidation temperature after irradiation. When the Si/SiO2structure is fabricated under different cooling rates, concentrations of thePbcenters are saturated after irradiation. The concentration ofE’centers increases with increasing cooling rate.