As the key element in the nuclear industry, uranium (U) has been widely concerned for its stable acquisition and efficient recycling. Capacitive deionization (CDI), which known as a seawater desalination technology, has shown great potential for uranium-adsorption. However, the poor selectivity restricts the application of CDI in uranium extraction. In this work, a carbonized MIP-202/MXene (CMM) composite was developed for highly efficient selective electrosorption of U(VI) from multi-ionic water. The uniformly decorated MIP-202 can prevent MXene from aggregation and provide rich pore structures, large specific surface area and additional nitrogen source for the efficient electrosorption of U(VI). With the addition of MXene nanosheets, a conductive network was introduced into the CMM and improved mechanical robustness of material to facilitate rapid charge transfer at the interface. As a result, the CMM electrode exhibited a maximum adsorption capacity of 582.46 mg g−1 calculated from Langmuir model and a removal ratio of 89.1% at 1.2 V in UO22+ solution. The selectivity adsorption of CMM for UO22+ can reach 92.3% when treated with multi-ionic solution. Besides, there is an interesting fact that the decreased ratio of added MXene can got a higher adsorption capacity, which may cause by the two composite structures formed when the mixing ratio changed. Overall, the excellent conductivity, high adsorption capacity and selectivity make CMM a promising electrode in CDI for efficient extraction of uranium from water.