It is of great significance to remove Cr(VI) from water as a result of its high toxicity. Biochar from corn straw was modified by different acids (HNO3, H2SO4 and H3PO4) to remove Cr(VI) from aqueous solution. To estimate the removal mechanisms of Cr(VI) by the acid-modified biochars, batch experiments were performed in the light of contact time, Cr(VI) concentration, and pH, and the characteristics of acid-modified biochars before and after Cr(VI) adsorption were investigated by Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS). The adsorption kinetics of Cr(VI) by acid-modified biochars were consistent with the pseudo-second-order model, and the adsorption isotherm obeyed the Freundlich model. Furthermore, the acid- modified biochars could supply more oxygen-containing functional groups (-COOH and -OH) as electron donor (e−) and hydrogen ion (H+) to enhance the reduction of Cr(VI) to Cr(III), resulting in enhanced removal of Cr(VI). HNO3-modified biochar exhibited the highest removal efficiency of Cr(VI). In general, the acid modifition of biochar was an effective method to increase the removal of Cr(VI).