This volume constitutes the refereed post-conference proceedings of the 5th International Conference on Machine Learning and Intelligent Communications, MLICOM 2020, held in Shenzhen, China, in September 2020. Due to COVID-19 pandemic the conference was held virtually. The 55 revised full papers were carefully selected from 133 submissions. The papers are organized thematically in intelligent resource ( spectrum, power) allocation schemes; applications of neural network and deep learning; decentralized learning for wireless communication systems; intelligent antennas design and dynamic configuration; intelligent communications; intelligent positioning and navigation systems; smart unmanned vehicular technology; intelligent space and terrestrial integrated networks; machine learning algorithm and Intelligent networks.