High‐pressure annealing (HPA) in both hydrogen (H2) and deuterium (D2) environments is attempted on HfO2/Si0.7Ge0.3 capacitors as a post‐metallization annealing (PMA) approach. As compared with conventional forming gas annealing (FGA), a dramatic reduction in the interface state density (Dit) is achieved after both H2‐ and D2‐HPA processes at the equivalent temperature (300 °C) and time (30 min) by effectively passivating the Ge‐induced dangling bonds at the interface region. Meanwhile, the stress‐induced leakage current characteristics are only improved by the D2‐HPA process, indicating that D‐passivation is more resistant to external electrical stress than H‐passivation. As the PMA temperature increases to 500 °C, both HPA further decreases the Dit, but a significant increase is observed for FGA. In addition, the PMA temperature‐dependent degradation of leakage current is less in HPA than in FGA.