Compressive stress in glass‐to‐metal seals is crucial to ensure sealing quality and service reliability. Photoluminescence spectroscopy (PS), which relies on the piezospectroscopic effect of Cr‐doped α‐Al2O3, shows promise for stress detection owing to its rapid detection, non‐destruction, and high resolution. The premise of the PS technique is to fill a glass matrix with alumina particles and detect signals from the alumina. In this study, the interaction between alumina particles and the glass matrix was analyzed to calibrate the measured stresses and investigate the stress state in the glass. Test results for glass‐to‐metal seals are believed to consist of simultaneous internal residual stress and external applied stress. The internal residual stress is formed due to the coefficient of thermal expansion mismatch between glass and alumina and is assumed to transfer by radial compression. In the experiment, it was detected by the PS technique and verified by X‐ray diffraction using an unstressed sample without metal housing. The external applied stress is formed due to metal housing compaction and possibly transferred by the shear effect. The stress distribution within the pre‐stressed sample containing metal housing was also measured by the PS technique. Then, calibrations were conducted on the measured stresses based on the deduced stress transfer relationships. Finally, finite element models were established to simulate the internal residual stress and external applied stress respectively to prove the validity of the calibration method, and mutually anastomotic results were obtained within the target margin of error.