In water purification, one of the major challenges is the selective removal of extremely hazardous Pb2+ from wastewater. Improving the Pb2+ removal capacity and selectivity of the transition metal oxide electrode is key to removing Pb2+ in CDI. Herein, TiVCTx MXene derived V-doped and C-modified TiO₂ cubic electrodes were synthesized using an in-situ interface growth-restriction strategy. The grain size and uniform distribution of TiO2 were effectively controlled by precisely regulating the chemical environment in the three-dimensional sub-nanometer confined space. Its solid solution structure permits uniform doping of V into the TiO₂ lattice, enhancing the material's electronic conductivity while providing active sites for redox reactions. Retaining the MXene carbon layer creates a TiO₂-loaded substrate that acts as a conductive network, which effectively improves the intrinsic conductivity of TiO2. Taking advantage of the synergistic effects mentioned above, the prepared V-TiO2/C electrodes exhibited excellent electro-chemical performance (214.1 F g−1), high Pb2+ storage capacity (134.7 mg g−1), and excellent Pb2+ selectivity (SPb/K = 71.9), superior to most reported transition metal oxide electrode materials. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) assisted reveals a Pb2+ removal mechanism dominated by dehydration redox with multiple mechanisms co-existing. This work provides an in-situ interface-restricted growth method for constructing efficient transition metal oxide electrodes.