The coarse pore system, interfacial transition zone (ITZ) between aggregate and paste matrix and volume fraction of unhydrated cement in concrete (w/c＝0.3) containing mineral admixtures were quantitatively characterized by the scanning electron microscope-backscattered electron (SEM-BSE) image analysis technique. The experimental results show that compound addition of slag and fly ash decreases the coarse porosity from 10.17% to 3.74% and the threshold diameter of coarse pore size from 345 µm to 105 µm compared with concrete (w/c＝0.30) without mineral admixtures; Moreover with compound addition of fly ash and slag, the volume proportion of unhydrated cement in paste matrix is reduced by 30%, the maximum amount of coarse pores in the ITZ between aggregate and paste decreases from 13.11% to 5.57% and the thickness of ITZ is reduced by 37% , compared with concrete without mineral admixtures.