Abstract: In this work, lawsone (LQ) and anthraquinone 2-sulphonate (AQS) (dissolved and covalently immobilized on activated carbon) were evaluated as redox mediators during the dark fermentation of glucose by a pretreated anaerobic sludge. Findings revealed that the use of dissolved LQ increased H₂ production (10%), and dissolved AQS improved H₂ production rate (11.4%). Furthermore, the total production of liquid byproducts (acetate, butyrate, ethanol, and butanol) was enhanced using dissolved (17%) and immobilized (36%) redox mediators. The established redox standard potentials of LQ and AQS suggested a possible interaction through electron transfer in cytochromes complexes for hydrogen production and the Bcd/EtfAB complex for volatile fatty acid formation.