Laser damage in films under long-term high-temperature conditions is a significant concern for advancing laser applications. This study focused on HfO2 films prepared using the sol–gel method with HfCl4 as a precursor. It examined the effects of temperature on various properties of the films, including their optical properties, microstructure, surface morphology, absorption, and laser-induced damage threshold (LIDT). The prepared film demonstrated desirable characteristics at the high temperature of 423 K, such as high transmittance, low absorption, and high LIDT. As the duration of its high-temperature exposure increased, the LIDT of the films gradually decreased. An intriguing finding was that the film’s LIDT exhibited an exponential decay pattern with prolonged heating time. This observation could be attributed to the power-law increase in defects on both the internal and surface areas of the film as the duration of high-temperature exposure lengthened. Moreover, even after a 15-day heating period at 423 K, the film maintained an LIDT of 12.9 J/cm2, indicating its potential applicability in practical high-temperature environments. This study provided a general pattern and a universal formula for understanding the laser damage of sol–gel films at high temperatures over time. Furthermore, it opened possibilities for future developments of laser films suitable for extreme environments.