Concrete suffers significant performance degradation when exposed to high temperatures. This study explored the beneficial role of waste glass powder (WGP) in mitigating thermal damage and ultra-high performance concrete (UHPC) after elevated temperature exposure. The mechanism was elucidated through the chemical and microstructure changes, the composition of hydrates after exposure to elevated temperatures, and the subsequent re-curing. The presence of WGP significantly enhanced the residual mechanical properties of UHPC due to more wollastonite generation. The WGP also facilitated the recovery of mechanical properties and surface morphology during the post-fire self-healing process. The microstructural results confirmed that the WGP promoted the formation of the wollastonite phase in the thermal-damaged UHPC by reacting with the dehydrated products. Thermodynamic simulations indicated that the incorporation of WGP in UHPC resulted in an increase of liquid phase and its early appearance at high temperatures led to the transformation of γ-C2S into more stable wollastonite phases. Meanwhile, the activation of unreacted WGP by limewater further generated secondary hydration products to reduce matrix porosity. These hydrates mainly consisted of C-(N)-S-H gels with a low calcium-to-silicon ratio (Ca/Si) and high sodium-to-silicon ratio (Na/Si) ratio, which could effectively fill the micropores and microcracks in UHPC. As a result, the densified microstructure induced by these regenerated C-(N)-S-H gels largely contributed to the recovery of the thermally damaged UHPC. The outcome of this study provides a decarbonization solution to address damages of UHPC exposed to fire conditions.