In this study, mechanical activation is used to generate ultra-fine fly ash (UFA) for high volume fly ash(FA)cement composites. The effects of different content and medium particle size of FA on mortar`s electrical resistivity, chloride penetration and mechanical properties are investigated. The results show that the compressive strength and resistance to chloride permeability of specimens with UFA have been enhanced, owing to higher pozzolanic reaction and higher dissolution rate of Si and Al units of UFA to accelerate the generate of reaction products. However, At the early ages, electrical resistivity of specimens increases with the increase of UFA; at later ages, specimens have a higher electrical resistivity with the increase of UFA.