Cr(III) adsorption by biochars generated from peanut, soybean, canola and rice straws is investigated with batch methods. Adsorption of Cr(III) increased as pH rose from 2.5 to 5.0. Adsorption of Cr(III) led to peak position shifts in the FTIR-PAS spectra of the biochars and made zeta potential values less negative, suggesting the formation of surface complexes between Cr3+ and functional groups on the biochars. The adsorption capacity of Cr(III) followed the order: peanut straw char > soybean straw char > canola straw char > rice straw char, which was consistent with the content of acidic functional groups on the biochars. The increase in Cr3+ hydrolysis as the pH rose was one of the main reasons for the increased adsorption of Cr(III) by the biochars at higher pH values. Cr(III) can be adsorbed by the biochars through electrostatic attraction between negative surfaces and Cr3+, but the relative contribution of electrostatic adsorption was less than 5%. Therefore, Cr(III) was mainly adsorbed by the biochars through specific adsorption. The Langumir and Freundlich equations fitted the adsorption isotherms well and can therefore be used to describe the adsorption behavior of Cr(III) by the crop straw biochars. The crop straw biochars have great adsorption capacities for Cr(III) under acidic conditions and can be used as adsorbents to remove Cr(III) from acidic wastewaters.