Biomass is gaining increased attention as a sustainable and low-cost hard carbon (HC) precursor. However, biomass properties are often unexplored and unrelated to HC performance. Herein, we used pine, beechwood, miscanthus, and wheat straw precursors to synthesize HCs at 1000 °C, 1200 °C and 1400 °C by a two-steps pyrolysis treatment. The final physicochemical and electrochemical properties of the HC evidenced dissimilar trends, mainly influenced by the precursor’s inorganic content, and less by the thermal treatment. Pine and beechwood HCs delivered the highest reversible capacity and coulombic efficiency (CE) at 1400 °C of about 300 mAh·g−1 and 80%, respectively. This performance can be attributed to the structure derived from the high carbon purity precursors. Miscanthus and wheat straw HC performance was strongly affected by the silicon, potassium, and calcium content in the biomasses, which promoted simultaneous detrimental phenomena of intrinsic activation, formation of a silicon carbide phase, and growth of graphitic domains with temperature. The latter HCs delivered 240−200 mAh·g−1 of reversible capacity and 70−60% of CE, respectively, at 1400 °C. The biomass precursor composition, especially its inorganic fraction, seems to be a key parameter to control, for obtaining high performance hard carbon electrodes by direct pyrolysis process.