Piezoelectric vibration sensors (PVSs) are widely used in high-temperature environments, such as vibration measurements in aero-engines, because of their high accuracy, small size, and high temperature resistance. Accurate prediction of its RUL (Remaining Useful Life) is essential for applying and maintaining PVSs. Based on PVSs’ characteristics and main failure modes, this work combines the Digital-Twin (DT) and Long Short-Term Memory (LSTM) networks to predict the RUL of PVSs. In this framework, DT can provide rich data collection, analysis, and simulation capabilities, which have advantages in RUL prediction, and LSTM network has good results in predicting time sequence data. The proposed method exploits the advantages of those techniques in feature data collection, sample optimization, and RUL multiclassification. To verify the prediction of this method, a DT platform is established to conduct PVS degradation tests, which generates sample datasets, then the LSTM network is trained and validated. It has been proved that prediction accuracy is more than 99.7%, and training time is within 94 s. Based on this network, the RUL of PVSs is predicted using different test samples. The results show that the method performed well in prediction accuracy, sample data utilization, and compatibility.