The zero-valent iron modified biochar materials are widely employed for heavy metals immobilization. However, these materials would be inevitably aged by natural forces after entering into the environment, while there are seldom studies reported the aging effects of zero-valent iron modified biochar. In this work, the hydrogen peroxide and hydrochloric acid solution were applied to simulate aging conditions of zero-valent iron modified biochar. According to the results, the adsorption capacity of copper(II) contaminants on biochar, zero-valent iron modified biochar-1, and zero-valent iron modified biochar-2 after aging was decreased by 15.36%, 22.65% and 23.26%, respectively. The surface interactions were assigned with chemisorption occurred on multi-molecular layers, which were proved by the pseudo-second-order and Langmuir models. After aging, the decreasing of capacity could be mainly attributed to the inhibition of ion-exchange and zero-valent iron oxidation. Moreover, the plant growth and soil leaching experiments also proved the effects of aging treatment, the zero-valent iron modified biochar reduced the inhibition of copper(II) bioavailability and increased the mobility of copper(II) after aging. All these results bridged the gaps between bio-adsorbents customization and their environmental behaviors during practical agro-industrial application.