Low-cost biochar adsorbent owning great potential for environmental remediation faces a bottleneck in application for its unsatisfied adsorption performance. Compared to the efforts on increasing adsorption capacity, improving adsorption speed which is important for treatment efficiency is often neglected. Herein, a hierarchical porous biochar (HPB) derived from shrimp shell was prepared and exhibited good adsorption capacity (Qm>300 mg/g) and fast adsorptive equilibrium (≤10 min) towards three typical aromatic organics, whose adsorption universality was further proved by two-way ANOVA analysis. Whereafter, model analysis demonstrated that, the adsorptive forms (mono- and multi-layers) on HPB depended on whether the contaminant is charged. Compared to the benzene-ring site of organics, the charged site contributed 5.13 times to adsorption promotion in monolayer but -0.49 times in inhibition for multilayers forms. Simultaneously, functional group sites contributed relatively weak (0.023 to 0.342 times only). Following structural control revealed that, hierarchical pore structure of HPB was the key for the fast adsorption speed, and highly graphitic structure was important for the high adsorption capacity. This study aims to provide an advanced biochar adsorbent, not only in adsorption capacity but also in adsorptive speed, and reveal the relationship between the structure and adsorption performance of biochar.