Heavy metal ions coexisting with salts in the contaminant water are difficult to remove due to the interference of salts. Herein, biochars were pyrolyzed by corn straw at different temperatures, aiming to remove Cr(VI) in the presence of salts. Results show that biochars had surprisingly selective adsorption of Cr(VI). X-ray photoelectron and X-ray absorption near edge spectra revealed that Cr(VI) was reduced to Cr(III). All the adsorption was conducted at pH similar to 7, which differed from the previous studies that Cr(VI) could only be reduced at pH 2-4. Environmental persistent free radicals (EPFRs) on biochars were found to play the role in reducing Cr(VI) in neutral solutions, which was confirmed by electron spin resonance and free radical quenching. The biochar with EPFRs reveals a highly selective removal of Cr(VI), which has implications for the remediation of contaminated water. This work provides a new insight into biochar's properties and potential environmental applications.