To exploit the outstanding ability of carbon nanotubes to facilitate electron transfer in a microbial fuel cell (MFC) system, multi-wall carbon nanotube (MWNT) and polyeletrolyte polyethyleneimine (PEI) were employed to modify carbon paper (TP) electrode utilizing a layer-by-layer (LBL) assemble technique for the first time, and the performance of the modified electrode as an anode in MFC was investigated. This modification strategy ensured a relatively high content of MWNTs within the polymer matrix. IR and cyclic voltammetry (CV) demonstrated the uniform formation of a polyethyleneimine/MWNT multilayer composite on the TP surface. The SEM profiles presented a three-dimensional MWNTs interwoven network surface structure with a large accessible surface area. Electrochemical impedance spectroscopy (EIS) measurements confirmed that the existence of polyelectrolyte/MWNT multilayers decreased the interfacial charge transfer resistance from 1163 to 258 Omega. With the modified anode, the MFC produced a higher power density with 20% enhancement comparing to the bare TP anode. The MWNT-based LBL self-assembled electrode is promising for the electricity production by MFC. (C) 2010 Elsevier Ltd. All rights reserved.