Two kinds of CACs with different monocalcium aluminate (CA) contents were used in the PC/CAC (PAC) mixtures. Effects of CA and CACs on the properties of PAC were analyzed by setting times and the compressive strength tests, and also by means of calorimetry, XRD, DTA-TG and ESEM. The experimental results show that the compressive strength of the PAC mortars decreases with increasing content of CAC while it declines sharply with a higher content of CA in CAC. Compared with neat PC paste, the content of calcium hydroxide in hydrates of PAC paste decreases significantly, and the hydration time of PC is prominently prolonged. Additionally, the higher the content of CA in CAC, the more obviously the hydration of PC is delayed, confirming that the CA phase in CAC plays an important role in the delay of PC hydration.