Cavitation in micro-scale lubricating film could be determined by the fluid’s thermal properties, which impacts the hydrodynamic lubrication capacity dramatically. This study aimed to novelly investigate the impact of the thermal cavitation effect on the hydrodynamic performance of liquid face seals, employing the compressible cavitation model, viscosity–temperature effect, and energy equation. The finite difference method was adopted to analyze the thermal cavitation by calculating the pressure and temperature profiles of the lubricating film. The working conditions and geometric configuration of liquid face seals under different thermal cases were further studied to explore their effects on sealing performance. The results showed that thermal cavitation could reduce the temperature difference of liquid film at high speeds, and cavitation would be weakened under temperature gradients, which further dropped off the hydrodynamic performance. Contrary to the leakage rate, the opening forces tended to be lower with the increasing seal pressure and film thickness under high-temperature gradients. Furthermore, apart from the spiral angle of grooves, the hydrodynamic performance exhibited significant variation with increasing groove depth, number, and radius at high-temperature gradients, which meant that the thermal cavitation effect should be considered in the design of geometric grooves to obtain better hydrodynamic performance.