Due to their large-scale production and extensive application, dyes have turned serious pollutants when improperly handled and disposed, creating grave public health and environmental problems. One of the problems that textile industry is facing is related with the incomplete exhaustion of dyes onto textile fibres from an aqueous dyeing process, and the need to implement innovative and sustainable effluent treatment methods to remove colour. Additionally, legislation on the limits of colour discharge has turn increasingly rigid. Biological treatment systems have been shown as promising technologies. The main limiting factor of the reductive transformations by anaerobic sludge is the electron transfer, a slow process. This limitation can be overcome by making use of redox mediators, which are compounds that accelerate the electron transfer from a primary electron donor to a terminal electron acceptor, to speed up the process. Activated carbon (AC) has been shown as a feasible redox mediator. Samples of microporous thermal treated AC (AC(H2)) and mesoporous carbons: xerogels (CXA, CXB) and carbon nanotubes (CNT) were tested on azo dye and textile wastewater biodegradation. similar to 85% Mordant Yellow 10 (MY10) and 70% of Reactive Red 120 (RR120) colour removal was obtained with all the carbon materials. Acid Orange 10 (AO10) is not biodegraded in the absence of carbon materials, but with CXB and CNT a 98% of colour removal was achieved. For MY10 and RR120, rates increased in the order: control < AC(H2) < CXA < CXB < CNT. HPLC analysis confirmed the reduction of dyes with the formation of corresponding aromatic amines. The effect of CNT was also observed in the biological treatment of real textile wastewaters. (C) 2013 Elsevier B.V. All rights reserved.