To solve the problems of high specific energy consumption and excessive harmful ions in the water production of a small reverse osmosis (RO) plant, a desalination system coupling RO and membrane capacitive deionization (MCDI) is proposed in this study. Aiming at producing two cubic meters per day of fresh water with a salt concentration of less than 280 mg L−1, parameter matching optimization was carried out on two desalination system schemes of one-stage two-section RO and one-stage three-section RO coupled with MCDI. The results were compared with the parameter matching optimization results of the one-stage one-section RO and the one-stage two-section pure RO desalination system. The results show that compared with the pure RO desalination mode, the seawater desalination mode coupled with RO and MCDI reduces the specific energy consumption under the same effluent salt concentration. Moreover, it decreases the feed water pressure in front of the RO membrane, which can reduce the standard of high-pressure pump in a small seawater desalination plant. The energy consumption of the one-stage three-section RO and MCDI coupling system is lower than that of the one- stage two-section RO and MCDI coupling system, and the feed water pressure is also lower.