Vehicular Edge Computing (VEC) is a promising paradigm to enable huge amount of data and multimedia content to be cached in proximity to vehicles. However, high mobility of vehicles and dynamic wireless channel condition make it challenge to design an optimal content caching policy. Further, with much sensitive personal information, vehicles may be not willing to caching their contents to an untrusted caching provider. Deep Reinforcement Learning (DRL) is an emerging technique to solve the problem with high-dimensional and time-varying features. Permission blockchain is able to establish a secure and decentralized peer-to-peer transaction environment. In this paper, we integrate DRL and permissioned blockchain into vehicular networks for intelligent and secure content caching. We first propose a blockchain empowered distributed content caching framework where vehicles perform content caching and base stations maintain the permissioned blockchain. Then, we exploit the advanced DRL approach to design an optimal content caching scheme with taking mobility into account. Finally, we propose a new block verifier selection method, Proof-of-Utility (PoU), to accelerate block verification process. Security analysis shows that our proposed blockchain empowered content caching can achieve security and privacy protection. Numerical results based on a real dataset from Uber indicate that the DRL-inspired content caching scheme significantly outperforms two benchmark policies.