This study reports the biosorption of Cr(VI) by chemically modified biomass of Rhizopus nigricans and the possible mechanism of Cr complexation to the adsorbent. The cell wall of this fungus possesses strong complexing property to effectively remove Cr(VI) anions from solution and wastewater. The mechanism of Cr adsorption by R. nigricans was ascertained by chemical modifications of the dead biomass followed by FTIR spectroscopic analysis of the cell wall constituents. Treatment of the biosorbent with mild alkalies (0.01 N NaOH and ammonia solution) and formaldehyde (10%, w/v) deteriorated the biosorption efficiency. However, extraction of the biomass powder in acids (0.1 N HCl and H 2 SO 4 ), alcohols (50% v/v, CH 3 OH and C 2 H 5 OH) and acetone (50%, v/v) improved the Cr uptake capacity. Reaction of the cell wall amino groups with acetic anhydride reduced the biosorption potential drastically. Blocking of the-COOH groups by treatment with water soluble carbodiimide also resulted in initial lag in Cr binding. Biomass modification experiments conducted using Cetyl Trimethyl Ammonium Bromide (CTAB), Polyethylenimine (PEI), and Amino Propyl Trimethoxy Silane (APTS) improved the biosorption efficiency to exceptionally high levels. The FTIR spectroscopic analysis of the native, Cr bound and the other types of chemically modified biomass indicated the involvement of amino groups of Rhizopus cell wall in Cr binding. The adsorption data of the native and the most effectively modified biomass were evaluated by the Freundlich and the Langmuir adsorption isotherms and the possible adsorption phenomena are also discussed.