To investigate the durability, especially the long-term stability of cement-based materials with very low w/b, the air permeability test, carbonation test, capillary absorption rate test and dilation Dotential test were adopted under long-term heat treatment condition. Microstructure of these materials is also analyzed by scannmg electronic microscopy (SEM) and mercury intrusion porosimeter (MIP) in order to further unveil its mechanism and interrelation between microstructure and its properties. The results indicate that in the area investigated, cement-based material with w/b 0.17, like RPC, possesses low porosity and excellent durability. Moreover, its porosity will further decrease under long-term heat treatment compared with normal heat treatment. Its long-term durability is much superior to that of other cement-based materials with w/b 0.25 or 0.35 as high strength concrete (HSC).