Conduction calorimetry was applied to an investigation of the early hydration of ordinary Portland cement (OPC)/high alumina cement (HAC) pastes. Three different rate of heat-evolution profiles were observed, depending on the HAC/OPC ratio. Relevant processes affecting heat development include ettringite formation, HAC and OPC hydration. Results from SEM examination and X-ray diffraction studies are also presented. An acceleration of OPC hydration was observed in pastes containing less than 12.5% HAC. A similar acceleration effect on HAC hydration was also obtained with the addition of OPC. A large amount of ettringite was formed and OPC hydration delayed in the pastes containing 15%-30% HAC. The latter could be one of the factors attributed to poor strength development in these HAC/OPC systems. Early hydration mechanisms of OPC/HAC systems are also discussed.