Conventional carbon-based electrodes like graphene are limited by costly, energy-intensive synthesis that rely on non-renewable precursors, challenging their scalability. While biomass-derived carbons (biochar) are a promising green alternative, achieving state-of-the-art performance typically requires chemical activation. Developing high-performance biochar through simple, scalable, and green pathways therefore remains a key challenge. In this work, we present a comprehensive physicochemical characterization of activation-free biochar derived from walnut, carob, rice husk and coffee via simple pyrolysis. Surface area, porosity and structural disorder were systematically analyzed to identify the key parameters governing ion interaction and charge storage. The results reveal a strong dependence of biochar properties on biomass type, with pronounced differences in accessible porosity and defect density. Among the materials studied, walnut-derived biochar combined a high specific surface area (1146 m²/g) with a high degree of structural disorder, highlighting the critical role of defects in enhancing ion adsorption and charge-transfer processes. Electrochemical measurements illustrated the functional implications of these intrinsic characteristics. Overall, this work demonstrates that carefully selected, unprocessed biomass can serve as a direct, low-cost source of functional carbon electrodes, providing insight into the parameters that dictate their electrochemical behavior and enable broader functional potential.