The adsorption behavior of mercury on Aspergillus versicolor biomass (AVB) has been investigated in aqueous solution to understand the physicochemical process involved and to explore the potentiality of AVB in pollution control management. This biomass has been successfully used for reducing the mercury concentration level in the effluent of chloralkali and battery industries to a permissible limit. The results establish that 75.6 mg of mercury is adsorbed per gram of biomass. The adsorption process is found to be a function of pH of the solution, with the optimum range being pH 5.0-6.0. The process obeys the Langmuir-Freundlich isotherm model. Scanning electron microscopic analysis demonstrates a conspicuous surface morphology change of the mercury-adsorbed biomass. A nearly uniform distribution of metal ions on the mycelial surface excepting a few aggregation points is revealed by X-ray elemental mapping profiles. The results of zeta potential measurement, Fourier transform infrared (FTIR) spectroscopy, and blocking of the functional groups by chemical modification reflect the binding of mercury on the biomass occurs through electrostatic and complexation reactions. The accumulation of mercury on the cell wall associated with negligible diffusion and or transportation into cytoplasm finds support from the results of adsorption kinetics and transmission electron micrographs. Mercury adsorption on biomass also leads to elongation of cells and cytoplasmic aggregation of spheroplast/protoplasts, indicating that the cell wall acts as a permeation barrier against this toxic metal.