Annihilation characteristics of positrons in the carbon/Si structure in thermal equilibrium at high temperature were studied using a monoenergetic positron beam. Doppler broadening spectra of the annihilation radiation were measured as a function of incident positron energy in the temperature range between 298 K and 1473 K. Above 1173 K, the value of S corresponding to the annihilation of positrons near the carbon/Si interface started to increase, which was attributed to the carbonization of Si and the introduction of open-space defects due to the diffusion of Si atoms toward the carbon layer. The behavior of Ps in a thermally grown SiO2 film was also studied at 298-1523 K.