AbstractIn this paper, chaos-guided artificial neural learning-based session key coordination for industrial internet-of-things (IIoT) to enhance the security of critical energy infrastructures (CEI) is proposed. An intruder might pose several security problems since the data are transferred across a public network. Although there have been substantial efforts to solve security problems in the IIoT, the majority of them have relied on traditional methods. A wide range of privacy issues (secrecy, authenticity, and access control) must be addressed to protect IIoT systems against attack. Owing to the unique characteristics of IIoT nodes, existing solutions do not properly address the entire security range of IIoT networks. To deal with this, a chaos-based triple layer vector-valued neural network (TLVVNN) is proposed in this paper. A chaos-based exchange of common seed value for the generation of the identical input vector at both transmitter and receiver is also proposed. This technique has several advantages, including (1) it protects IIoT devices by utilizing TLVVNN synchronization to improve CEI security. (2) Here, artificial neural coordination is utilized for the exchange of neural keys between two IIoT nodes. (3) Using this suggested methodology, chaotic synchronization can be achieved, enabling the chaos-based PRNG seed exchange. (4) Vector-valued inputs and weights are taken into consideration for TLVVNN networks. (5) The deep internal architecture is made up of three hidden layers of the neural network and a vector value as input. As a result, the attacker would have great difficulty interpreting the internal structure. Experiments to verify the performance of the proposed technique are conducted, and the findings demonstrate that the proposed technique has greater performance benefits than the existing related techniques.