The present work adopted powdered activated carbon (PAC) as ballasting agent to achieve robust separation effect and efficiency of bio-refractory DOM from the bio-chemically treated cassava distillery wastewater (BTDWW). More than 90% of DOC could be removed at the PAC and Fe(III)-coagulant dosage of 1.40 g/L and 0.84 g/L as Fe when the BTDWW was neutral. PAC should be dosed before coagulant in order to mix well with the DOM in the BTDWW. The analyses of DOM in effluent reveal that PAC facilitated the removal of lignin breakdown products which could not be well eliminated by regular coagulation; the removal of DOM with MW < 5 kDa was mostly enhanced. The characteristics of flocs demonstrate that PAC reinforced the interaction between Fe(III) species and DOM by providing more reaction sites. The sedimentation could be completed within the initial 5 min, and the highest settling velocity was almost 8 times higher than that of the only Fe(III)-involved flocs. The large size and favorable robustness of PAC-involved flocs enabled decent sedimentation even though their stretched structure might not be desirable in regular coagulation. The PAC-ballasted coagulation is recommended as tertiary treatment of BTDWW considering its high efficiency and sound economic feasibility.