The present study highlights the application of perfluorooctyl bromide (PFOB), an oxygen carrier, in a fixed-film membrane gradostat reactors (MGRs) in which biofilms of Phanerochaete chrysosporium BKMF-1767 (ATCC 24725) were immobilised. The nutrient medium used in the MGRs was supplemented with PFOB and Pluronic F 68 (PF 68) to alleviate limitations associated with the performance of the immobilised fungus. Lower lignin peroxidase production in PFOB/PF 68 cultures was observed compared to manganese peroxidase production, suggesting an insignificant generation of reactive oxygen species (ROS). Lipid peroxidation, quantified by the formation of malondialdehyde, was lower in the immobilised cultures. After successfully applying PFOB and PF 68 to immobilised P. chrysosporium biofilms in the MGRs, the following results were obtained: [1] reduced ethanol production, [2] reduced trace element accumulation, [3] lower β-glucan production and [4] an improved dissolved oxygen penetration ratio in the immobilised biofilms.