The hydration behavior of fly ash and slag on cement paste were investigated. Early stage of hydration reaction was delayed by mixing fly ash and/or slag with cement, but production of C-S-H hydrates by pozzolanic reaction densified the microstructure. The Ca/Si ratio of C-S-H hydrates in OPC and blended cement of fly ash 50%, slag 50%, fly ash+slag 50% were 2.24, 1.80, 1.82 and 1.97, respectively. The C-S-H gel with low Ca/Si ratio showed rather reticulate than needle-like structure.