An exoelectrogenic culture was enriched on 1.0 g/L xylose from a compost sample in two-chamber microbial fuel cells (MFCs). Electricity production was optimized by changing mixing type, external resistance, xylose concentration and pH. Furthermore, the changes in microbial communities after each optimization step were monitored with PCR-DGGE. Electricity production was highly dependent on operational conditions that affected power densities (PD), Coulombic efficiencies (CE), substrate degradation, utilization of soluble metabolites for electricity production and stability of MFC performance. The optimum operational conditions for electricity production were without mixing, 100 Omega external resistance, 0.5 g/L xylose and pH 7. With optimized operational conditions PD of 590 mW/m(2) and CE of 82% were obtained. Microbial community composition, consisting mainly of Geobacter sulfurreducens, Escherichia coli, Sphaerochaeta sp. TQ1 and Bacteroides species, was mainly affected by MFC configuration, i.e. electrical connections, which likely affected the anode potential. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.