The development and utilization of biomass and agroforestry processing byproducts for high-value applications have been an important topic in the field of renewable materials research. Based on this, a two-step microwave hydrothermal pre-carbonization and KOH activation method was proposed to synthesize tannin-based activated carbons with a high specific surface area, hierarchical pore structure, and good electrochemical performance. The microstructure, texture properties, and physicochemical characteristics were investigated. The results show that the prepared tannin-based activated carbons presented a hierarchical pore structure (micro-and mesopores) with a specific surface area as high as 997.46 m 3 g −1 . The electrochemical analysis shows that the tannin-based activated carbons have good wettability and charge transfer rates. Under the three-electrode system with 6 M KOH as the electrolyte, the active material TAC 600-4 had a maximum specific capacitance of 171 F g −1 at 0.5 A g −1 . As the current density increases to 10 A g −1 , the specific capacitance can still be maintained at 149 F g −1 , indicating a good rate capability. Therefore, the specific surface area and pore size of tannin-based activated carbons can be effectively adjusted by the alkali/carbon ratio, making it a promising supercapacitor electrode material and providing a new method for the high-value development of tannins in the field of electrochemical energy storage.