Recently, significant research attention has been devoted to the study of reconfigurable intelligent surfaces (RISs), which are capable of reconfiguring the wireless propagation environment by exploiting the unique properties of metamaterials-based integrated large arrays of inexpensive antennas. Existing research demonstrates that RISs significantly improve the physical layer performance, including the wireless coverage, achievable data rate and energy efficiency. However, the medium access control (MAC) of multiple users accessing an RIS-enabled channel is still in its infancy, while many open issues remain to be addressed. In this article, we present four typical RIS-aided multi-user scenarios with special emphasis on the MAC schemes. We then propose and elaborate upon centralized, distributed and hybrid artificial-intelligence (AI)-assisted MAC architectures in RIS-aided multi-user communications systems. Finally, we discuss some challenges, perspectives and potential applications of RISs as they are related to MAC design.