An anodic syntrophic consortium (exoelectrogenic plus fermentative bacteria) able to use methanol as sole carbon source was developed for the first time in a bioelectrochemical system. In this frame, promising results were obtained in single chamber MFC, comparable to those obtained with readily biodegradable substrates. Regarding MEG operation, the presence of homoacetogenic bacteria led to electron recycling, avoiding net hydrogen production in single chamber MEC. In a double chamber MEC, satisfying results (in terms of coulombic efficiency and cathodic gas recovery) were obtained even though energy recovery still restrained the feasibility of the process. The approach used in this work with methanol opens a new range of possibilities for other complex substrates as electron donors for bioelectrosynthesis. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.