Microorganisms from paddy soils and raw hematite are used for enhancing natural Fe(III) bio-reduction, in order to remove macromolecular organic pollutants from humified landfill leachate. Based on batch experiments, 60% of refractory organics can be adsorbed by hematite in 12 days. In the presence of Fe(III)-reducing bacteria, 489.60 +/- 0.14 mg L-1 of dissolved organic matters can be degraded to 51.90 +/- 3.96 mg L-1 within 50 days; twelve types of semi volatile organic compounds can be degraded; hereby, the reaction follows a first-order kinetics. Crystalline Fe(III) is transformed into the amorphous form and reduced to Fe(II), hydroquinone functional groups in the humic acid (HA) are transformed to quinone ones, and the formation of HA-hematite ligands is promoted. Comparing with most of the studies about electron shuttling of HA, the transformation of quinone in the HA to hydroquinone could not be observed in the present bio-system. Based on column evaluations, more than 93% of chemical oxygen demand (influent concentration of 658 +/- 19 mg L-1) could be removed microbially under flow conditions, when the hydraulic retention time was 45 h. Raw hematite-based Fe(III) bio-reduction has a promising potential for the removal of humic and benzene series in humified landfill leachate.