To solve the privacy leakage problem faced by Internet of Vehicles (IoV) users when enjoying location-based services (LBS), a privacy-protecting predictive cache method based on blockchain and machine learning (BML-PPPCM) is proposed. First, a Bi-directional Long-Short Term Memory (Bi-LSTM) model is used to predict query requests over a future period based on historical request information. The predicted results are recommended to neighbors and broadcast to requestors. Then, deep Q-learning (DQN) is utilized to determine the optimal cache decision. Finally, a trust mechanism is introduced to calculate trust values, and blockchain is used to store transaction data and trust data, preventing malicious tampering by attackers. The simulation results show that BML-PPPCM has a higher cache hit ratio than other similar schemes and performs well in privacy protection and suppression of malicious and incentive denial of service providers.