The aim of this study was to investigate the Cr(VI) biosorption potential of immobilized Rhizopus nigricans and to screen a variety of non-toxic desorbing agents, in order to find out possible application in multiple sorption-desorption cycles. The biomass was immobilized by various mechanisms and evaluated for removal of Cr(VI) from aqueous solution, mechanical stability to desorbents, and reuse in successive cycles. The finely powdered biomass, entrapped in five different polymeric matrices viz. calcium alginate, polyvinyl alcohol (PVA), polyacrylamide, polyisoprene, and polysulfone was compared for biosorption efficiency and stability to desorbents. Physical immobilization to polyurethane foam and coir fiber was less efficient than polymer entrapment methods. Of the different combinations (%, w/v) of biomass dose compared for each matrix, 8% (calcium alginate), 6% (polyacrylamide and PVA), 12% (polyisoprene), and 10% (polysulfone) were found to be the optimum. The Cr sorption capacity (mg Cr/g sorbent) of all immobilized biomass was lesser than the native, powdered biomass. The Cr sorption capacity decreased in the order of free biomass (119.2) > polysulfone entrapped (101.5) > polyisoprene immobilized (98.76) > PVA immobilized (96.69) > calcium alginate entrapped (84.29) > polyacrylamide (45.56), at 500 mg/I concentration of Cr(VI). The degree of mechanical stability and chemical resistance of the immobilized systems were in the order of polysulfone > polyisoprene > PVA > polyacrylamide > calcium alginate. The bound Cr(VI) could be eluted successfully using 0.01 N NaOH, NaHCO3, and Na2CO3. The adsorption data for the native and the immobilized biomass was evaluated by the Freundlich isotherm model. The successive sorption-desorption studies employing polysulfone entrapped biomass indicated that the biomass beads could be regenerated and reused in more than 25 cycles and the regeneration efficiency was 75-78%.