Biosorption has been demonstrated to be a useful alternative to conventional treatment systems for the removal of toxic metals from dilute aqueous solution. The objective of this paper was to examine the main aspects of a possible strategy for the removal of arsenates, employing P. chrysogenum biomass. The pretreatment of biomass with common surfactants (as hexadecyl-trimethylammonium bromide and dodecylamine) and a cationic polyelectrolyte was found to improve the biosorption efficiency. The initial biomass showed a relative low affinity for metallic anions, whereas with the application of modified samples a significant uptake of arsenic was observed. Sorption data were well described by typical Langmuir and Freundlich adsorption isotherms. Promising results were obtained in laboratory experiments and effective As(V) removals were observed.