Tannery sludge with high chromium content has been identified as hazardous solid waste due to its potential toxic effects. The safety disposal and valorization of the tannery sludge remains a challenge. In this study, the chromium stabilization mechanism was systematically investigated during chromium-rich tannery sludge was converted to biochar and the removal performance of the sludge biochar (SBC) for Cr(VI) from tannery wastewater was also investigated. The results showed that increase in pyrolysis temperature was conductive to the stabilization of Cr and significant reduction of the proportion of Cr(VI) in SBC. It was confirmed that the stabilization of chromium mainly was attributed to the embedding of chromium in the C matrix and the transformation of the chromium-containing substances from the amorphous Cr(OH)₃ to the crystalline state, such as (FeMg)Cr₂O₅. The biochar presented high adsorption capacity of Cr(VI) at low pH and the maximal theoretical adsorption capacity of SBC produced at 800°C can reach 352 mg Cr(VI)/g, the process of which can be well expressed by Langmuir adsorption isotherm and pseudo second order model. The electrostatic effect and reduction reaction were dominantly responsible for the Cr(VI) adsorption by SBC800. Overall, this study provided a novel strategy for the harmless disposal and resource utilization for the solid waste containing chromium in leather industry.