In this paper, CMOS technology-based neural session key generation is proposed for integration with the Internet-of-Things (IoT) to enhancing security. Recent technological developments in the IoT era enable improved strategies to exacerbate the maintenance of energy efficiency and stability issues. The existing security solutions do not properly address IoT’s security. A small logic area ASIC implementation of a re-keying enabled Triple Layer Vector-Valued Neural Network (TLVVNN) using CMOS architectures with measurements of 65 and 130 nanometers are proposed for integration with IoT. The paper aims to defend IoT devices using TLVVNN synchronization to enhance security. For a 20% weight misalignment in the re-keying phase, the synchronization period may be decreased from 1.25 ms to less than 0.7 ms, according to behavioral simulations. Experiments to verify the proposed technique’s performance are conducted, and the findings demonstrate that the proposed method has greater performance benefits than the existing related techniques.