1-3 type cement/epoxy resin based piezoelectric composite was designed and fabricated aiming at providing a new method for cement hydration monitoring. Combining with piezoelectric impedance technology, the cement hydration reaction process was monitored by using the composite. The research results show that in the initial cement hydration period, the resistance-frequency curves of the sensor drift toward low frequency direction, while the anti-resonance resistance value decreases gradually. With increasing cement hydration time, the resistance-frequency curves of the sensor drift toward high frequency direction and the anti-resonance resistance value shows fluctuation changes. The cement hydration reaction process can be divided into different periods according to changes of anti-resonance frequency and anti-resonance resistance value of the sensor.