AbstractSolar thermal energy is a technology that collects radiant energy from the sun to generate heat or electricity. Thermal energy storage is required to compensate for the solar thermal energy variations across time scales, and a popular strategy is storing thermal energy in hot water tanks. Due to superior strength and durability, ultrahigh-performance concrete (UHPC) is exploited to construct such water tanks for applications at 200°C. Therefore, the mechanical strength and microstructure of UHPC after long-term temperature-pressure load (autoclaving) is studied. The compressive strength of UHPC can stay robust due to the accelerated formation of hydrates, while the flexural strength is vulnerable to long-term autoclaving due to the transformation of amorphous calcium silicate hydrate (C-S-H) to more ordered phases. The main hydrates in autoclaved samples are poorly crystallized C-S-H, hydroxylellestadite, and hydrogarnet. The porosity of autoclaved samples is not strictly related to the mechanical strength, and the influence of hydrate assemblage outweighs that of porosity on mechanical strength after long-term autoclaving. The partial replacement of cement by limestone powder can decrease crystalline hydrates and increase poorly crystallized C-S-H, which densifies the microstructure and enhances the mechanical strength. However, excessive poorly crystallized C-S-H aggravates the thermal mismatch between the matrix and quartz aggregates after autoclaved samples cool to room temperature, leading to interstice in matrix-quartz interfaces and, thus, reduced mechanical strength. Therefore, an appropriate addition of limestone powder is required to induce the hydrate assemblage with appropriate poorly crystallized C-S-H, ensuring durable UHPC structures under autoclaving.