Biochar derived from lignocellulosic biomass has been used as a low-cost adsorbent in wastewater treatment applications. Due to its rich porous structure and good electrical conductivity, biochar can be used as a cost-effective electrode material for capacitive deionization of water. In this work, willow biochar was prepared through carbonization of shrub willow chips, activated with potassium hydroxide, and loaded with manganese dioxide (WBC-K-MnO2 nanocomposite). The prepared materials were used to electrochemically adsorb Pb2+ from aqueous solutions. Under the applied potential of 1.0 V, the WBC-K-MnO2 electrode exhibited a high Pb2+ specific electrosorption capacity (23.3 mg/g) as compared to raw willow biochar (4.0 mg/g) and activated willow biochar (9.2 mg/g). KOH activation followed by MnO2 loading on the surface of raw biochar enhanced its BET surface area (178.7 m(2)/g) and mesoporous volume ratio (42.1%). Moreover, the WBC-K-MnO2 nanocomposite exhibited the highest specific capacitance value of 234.3 F/g at a scan rate of 5 mV/s. The electrosorption isotherms and kinetic data were well explained by the Freundlich and pseudo-second order models, respectively. The WBC-K-MnO2 electrode demonstrated excellent reusability with a Pb2+ electrosorption efficiency of 76.3% after 15 cycles. Thus, the WBC-K-MnO2 nanocomposite can serve as a promising candidate for capacitive deionization of heavy metal contaminated water.