An electrodeless resistivity measurement system developed recently can provide a reliable method for monitoring the hydration process of cement-based materials continuously and accurately. Phosphoaluminate cement (PAC) sets quickly and develops high early strength. In order to understand the mechanism, the hydration products and microstructure formation of PAC in early age need to be studied. In the study, early hydration process of PAC with different dosage of retarder was investigated by the electrodeless resistivity equipment. According to resistivity-time curve, resistivity of freshly mixed PAC paste decreases sharply and then rises slowly, some characteristic peaks appear at different hydration stages of PAC. Heat evolution of PAC was also measured. The hydration mechanism and structure formation were studied according to these results. Depending on the dosage of retarder, the hydration process of PAC includes four stages which are dissolution, induction, acceleration and deceleration.