Reconfigurable intelligent surface (RIS) is a promising reflective radio technology for improving the coverage and rate of future wireless systems by reconfiguring the wireless propagation environment. The current work mainly focuses on the physical layer design of RIS. However, enabling multiple devices to communicate with the assistance of RIS is a crucial challenging problem. Motivated by this, we explore RIS-assisted communications at the medium access control (MAC) layer and propose an RIS-assisted MAC framework. In particular, RISassisted transmissions are implemented by pre-negotiation and a multi-dimension reservation (MDR) scheme. Based on this, we investigate RIS-assisted single-channel multi-user (SCMU) communications. Wherein the RIS regarded as a whole unity can be reserved by one user to support the multiple data transmissions, thus achieving high efficient RIS-assisted connections at the user. Moreover, under frequency-selective channels, implementing the MDR scheme on the RIS group division, RISassisted multi-channel multi-user (MCMU) communications are further explored to improve the service efficiency of the RIS and decrease the computation complexity. Besides, a Markov chain is built based on the proposed RIS-assisted MAC framework to analyze the system performance of SCMU/MCMU. Then the optimization problem is formulated to maximize the overall system capacity of SCMU/MCMU with energy-efficient constraint. The performance evaluations demonstrate the feasibility and effectiveness of each