The present work adopted a novel microbubble system - Fe(III)-coagulant-modified colloidal gas aphrons (CGAs) in flotation as tertiary treatment of the bio-chemically treated cassavadistillery wastewater. Approximately 93% of bio-recalcitrant color and around 79% of dissolved organic carbon (DOC) were removed at the initial pH of 9.0 and 7.1, individually. The modified CGAs exhibited strong ability of complexation and electrostatic attraction of the polyanions of DOM and colorants. But the 1-10 kDa DOM was found to be resistant to the CGA capture. Compared with directly dosing coagulant, the Fe(III)-coagulant-modified CGAs consumed ∼47% and ∼21% less coagulant to achieve the optimum decoloration efficiency and DOC removal, respectively. In the flotation with Fe(III)-coagulant-modified CGAs, the coagulant-dosing system could be omitted while the coagulant utilization was improved.