High performance concrete (HPC) with a water/cement ratio (w/c) of 0.32 and different lightweight aggregate (LWA) contents (0%, 25%, 50%, 75%, 100%) were prepared, and the influence of LWA on concrete frost-resistance and impermeability at different ages were studied, as well as the hydration degree, hydrated product, pattern and pore structure of the paste around aggregate. The results show that, by replacing normal weight aggregate (NWA) with 50% and 100% volume contents of pre-wetted LWA respectively, the chemical bound water of the cement paste surrounding aggregate are increased 12.1% and 22.7% as compared to concrete mixed without LWA. And at 28 days, lightweight aggregate concrete has the highest Ca(OH)2 content, whereas the 90-day Ca(OH)2 content of normal weight concrete is the highest. This proves that, with the increase of LWA content in concrete, both of the internal curing effect of pre-wetted LWA and secondary hydration effect of fly ash (FA) are strengthened, this can also be verified by the SEM study. Furthermore, the pore structure of the cement paste around aggregate can be improved consequently. The performance of frost-resistance of HPC can be improved by mixing LWA, the 90 day-frost-resistance of lightweight aggregate concrete is about 2.5 times of that of concrete mixed without LWA. The influence of LWA on the impermeability of HPC is different from normal concrete. When LWA content is more than 50%, the HPC impermeability decreased obviously, however at later age the difference between them becomes minor.