In this work, hickory chip biochars developed at distinctive pyrolysis temperatures were ball milled (BMHC) and then post-modified with a 10% hydrogen peroxide (H2O2) solution to obtain a set of novel sorbents (BMHC-H2O2). The specific surface area (SSA) was dramatically increased after ball-milling while the hydroxyl and carboxyl groups on the surface of the biochars were further increased through H2O2 modification. Additionally, thermal stability of the biochar treated with ball-milling was not greatly reduced by H2O2 modification and hydrodynamic radius was decreased. Ball milling enhanced the adsorption efficiency to methylene blue (MB) by the biochar, and this ability was further increased by H2O2 modification, because of the increasing in oxygen-containing functional groups (OCFG) to interact with MB. The rate of MB adsorption to BMHC-H2O2 was faster than that of BMHC, reaching equilibrium after about 6 h. Among adsorbents tested, the 450 °C BMHC-H2O2 had the greatest MB adsorption capacity (310 mg g−1).