This research aimed to investigate the influence of high-volume mineral admixtures (MAs), i.e., fly ash and slag, on the hydration characteristics and microstructures of cement pastes. Degree of cement hydration was quantified by the loss-on-ignition technique and degree of pozzolanic reaction was determined by a selective dissolution method. The influence of MAs on the pore structure of paste was measured by mercury intrusion porosimetry. The results showed that the hydration properties of the blended pastes were a function of water to binder ratio, cement replacement level by MAs, and curing age. Pastes containing fly ash exhibited strongly reduced early strength, especially for mix with 45% fly ash. Moreover, at a similar cement replacement level, slag incorporated cement paste showed higher degrees of cement hydration and pozzolanic reaction than that of fly ash incorporated cement paste. Thus, the present study demonstrates that high substitution rates of slag for cement result in better effects on the short- and long-term hydration properties of cement pastes.