The design and synthesis of high‐performance and economical carbon electrodes play a critical role in developing energy‐efficient water desalination technologies. As a sustainable approach, low‐cost and abundant biomass materials are promising candidates to prepare porous carbon for capacitive deionization. In this study, binder‐free porous carbon sheets are successfully prepared using natural balsa, pine, and basswood by thermal carbonization and treated by chemical activation. The carbon electrode materials converted from balsa and pine exhibit a comparable salt adsorption performance by capacitive deionization due to the extensive surface area, substantial electrical property, and superior hydrophilic performance. The following activation treatment of the balsa‐converted carbon further enhances the surface and electrical properties and benefits the desalination performance. The salt adsorption capacity of the activated balsa electrode exhibits 12.45 mg g−1. Additionally, 19.52 mg g−1 Pb2+ and 20.06 mg g−1 Cr3+ heavy metal adsorption capacity is also observed with the activated balsa electrode in 100 mg L−1 PbCl2 and 50 mg L−1 CrCl3, respectively. To the best of authors’ knowledge, this is the highest NaCl adsorption capacity performance reported thus far by using pure wood converted carbon as the electrode, and these promising results indicate that activated balsa is an extraordinary material for water desalination.

For most electrodes fabricated with carbon, transition metal compounds, or conductive polymers, the capacitance may deteriorate with cyclic charging and discharging. Thus, an electrochemically stable supercapacitor has long been pursued by researchers. In this work, the hierarchical structure of balsa wood is preserved in the converted carbon which is used as a supporting framework to fabricate electrodes for supercapacitors. Well‐grown carbon nanotubes (CNTs) on interior and exterior surfaces of balsa carbon channels provide two advantages including 1) offering more specific surface area to boost capacitance via electric double layer capacitance and 2) offering more active Fe and Ni sites to participate in the redox reaction to enhance capacitance of the balsa carbon/CNTs electrode. The balsa carbon/CNTs demonstrate an excellent area capacitance of 1940 mF cm−2. As active sites on Ni and Fe catalysts and inner walls of CNTs are gradually released, the capacitance increases 66% after 4000 charge–discharge cycles. This work brings forward a strategy for the rational design of high‐performance biomass carbon coupled with advanced nanostructures for energy storage.