The use of agricultural byproducts and industrial biowaste materials has been shown to be an attractive technique for removing Cr(VI) from contaminated waste waters. In this study, used brewers draff, peat moss, sawdust, grape stalks and husks were investigated as novel biosorbents for Cr(VI). The material was tested in two different modifications. The material was dried, cut and sieved and part of it was subjected to acid (2 M H2SO4) and alkali (0.5 M NaOH) pre-treatments to remove starch, proteins and sugars. Fourier transform infrared rays analysis on solid phase (FTIR-ATR) was used to determine the main functional groups that might control the metal uptake. Batch experiments were performed at different pH values (3, 4.5, 6) and at various initial concentration of Cr(VI) (25–2012;250 mg L 1). Two equilibrium empirical models, Langmuir and Freundlich, were used to describe Cr(VI) adsorption. In order to identify possible reduction processes, ion exchange separation on the AG1-X8 resin was used to separate the anionic Cr(VI) and the reduced cationic Cr(III) from the aqueous phase after biosorption. As expected, Cr(VI) removal was pH-dependent and fitted well both the Langmuir and Freundlich isotherm models. The ion exchange separation showed that Cr(VI) reduction had occurred in the solution during biosorption. The efficiency of draff as a biosorbent was comparable (or even higher) to highly organic materials (e.g., composted peat) showing its potential application for Cr(VI) decontamination.