The dynamics of residual stress (RS) within glass-to-metal (GTM) seals play a crucial role in their operational efficacy, with the progression of RS in response to temperature variations being a critical aspect in engineering applications. This research utilizes fiber Bragg grating sensors and temperature-calibrated photoluminescence spectroscopy techniques for the in situ monitoring of RS changes within GTM seals during heating. Initially, the glass body exhibited a compressive stress of −203 MPa, while the stress in the glass close to the interface was −367 MPa at room temperature. With increasing temperature, RS within both the glass body and in the glass close to the interface transitions through three distinct phases: a near-linear decrease, a rapid decrease, and a shift from compressive to tensile stress. By 540 °C, tensile stresses of approximately 11 MPa within the glass body and 36 MPa in the glass close to the interface were observed. The study elucidates that RS evolution is intricately linked not only to the thermal expansion properties of the constituent materials but also to the β-relaxation phenomenon within the glass structure and the presence of an oxide layer at the interface. Finite-element analysis simulations were conducted to corroborate the experimental findings, illustrating a congruent RS evolution pattern and delineating the transition from a compressive to a tensile state. This investigation provides empirical data and analytical insights concerning the management of RS in GTM seals, underscoring the significance of RS control in maintaining seal integrity.