This paper evaluates heterotrophic leaching of arsenic (As) pre-adsorbed onto amorphous ferric o x y hy d r o x i d e s ( F e O x ) a nd i t s su b s e q ue n t biovolatilization under laboratory conditions during Aspergillus niger static cultivation. With initial 90 mg.L −1 As concentration and absence of FeOx, the biomass As accumulation capacity attained 1.4 mg.g −1 on the 15th day of cultivation. While FeOx suppressed As biomass accumulation up to 0.23 mg.g −1 , it did not influence biovolatilization activity. After 15-day cultivation, almost 1.8 mg As was released into the surrounding culture media, accumulated and subsequently transformed into its volatile derivatives, regardless of FeOx presence or absence. The A. niger strain was able to enhance As release from the FeOx surfaces; the total As medium concentration increased to 3.1 mg.L −1 on the 15th cultivation day, and this amount was considerably higher than the 0.128 mg.L −1 As concentration leached from FeOx in fungal absence. These observations indicate that complex mutual interactions between As immobilized in FeOx and filamentous fungi are environmentally significant regarding As mobility and transformation in oxic environments.