Abstract This paper proposes an advanced encryption standard (AES) cryptosystem based on memristive neural network. A memristive chaotic neural network is constructed by using the nonlinear characteristics of a memristor. A chaotic sequence, which is sensitive to initial values and has good random characteristics, is used as the initial key of AES grouping to realize "one-time-one-secret" dynamic encryption. In addition, the Rivest-Shamir-Adleman (RSA) algorithm is applied to encrypt the initial values of the parameters of the memristive neural network. The results show that the proposed algorithm has higher security, a larger key space and stronger robustness than conventional AES. The proposed algorithm can effectively resist initial key-fixed and exhaustive attacks. Furthermore, the impact of device variability on the memristive neural network is analyzed, and a circuit architecture is proposed.