Digital manufacturing in Industry 5.0 aims to provide resource-efficient and user-preferred manufacturing processes by combining the innovative thinking of human specialists with precise, smart, and effective technologies. A significant digital manufacturing strategy that has recently experienced fast growth is additive manufacturing (AM). Additionally, artificial intelligence (AI) is being used more and more in the design, production, and assessment phases of AM product development. This opens new possibilities for the development of affordable, human-centered goods. In fact, these days, more and more human-centered products and customized devices, are being made using AM. The accreditation and certification process for AM has slowed down the technology’s rapid growth despite the numerous weaknesses seen in the produced items. Thus, current challenges in AM research are oriented in the AI-enabled customized design, production, and control-evaluation of AM processes. Also, AI-enabled AM materials design is a fundamental part of the revolution and advancement of AM. This chapter provides a discussion of obstacles and research prospects for wider AI use in AM applications, especially for human-centered AM solutions, and the advances and attended revolutions in AM materials and processes guided and supported by Industry 5.0 enabling technologies, such as artificial neural networks, edge computing, or machine learning. Finally, a simple case study is presented to underline how commercial AI systems such as ChatGPT can enhance and empower AM design and printing process, also without AI training.