Ultrasonic waves provide a non-destructive and sensitive way to monitor the concrete hydration. However, limited works are reported to monitor the evolution of the mechanical parameter at early ages. In this study, modified piezoelectric aggregates are embedded inside a concrete beam to excite and receive primary waves. A hydration index, namely, the variation of ultrasonic waveform (VUW) is developed to characterize the variation of the transmitted waves during the hydration process. The recorded hydration indices are compared with the compressive strength measured by destructive test at different ages. The results show that the VUW is closer to the compressive strength than the other two traditional hydration indices, ultrasonic velocity and wave packet energy. The proposed VUW provides a simple and accurate way to monitor the concrete hydration at early ages.