The residual stress introduced inside the thermal barrier coating (TBC) top coating during manufacturing and service processes is one of the main causes of thermal barrier failure. Therefore, a nondestructive and accurate measurement of the residual stress in top coating is essential for the evaluation of TBC life. The terahertz time-domain spectroscopy (THz-TDS) technique, which is based on the calibration or measurement of the stress optical coefficients of the measured materials, is applicable to the measuring of internal stress of nonmetal materials. In this work, to characterize the internal stress in TBC, the stress optic coefficient of the TBC top coating was measured by reflection-type THz-TDS. First, the mechanics model for the internal stress measurement in a TBC top coating was derived based on the photoelastic theory. Then, the THz time-domain spectra of TBC specimens under different loadings were measured in situ by a reflection-type THz-TDS system. Finally, the unimodal fitting, multimodal fitting and barycenter methods were used to carry out the data processing of the THz time-domain spectral-characteristic peaks. By comparing the processed results, the results using the barycenter method were regarded as the calibrated stress optical coefficient of the TBC due to the method’s sufficient accuracy and stability.