Layered carbon fiber mats have been prepared by layer-by-layer (LBL) electrospinning of polyacrylonitrile onto thin natural cellulose paper and subsequent carbonization. The layered carbon fiber mat has been proved to be a promising microbial fuel cell anode for high density layered biofilm propagation and high bioelectrocatalytic anodic current density. (C) 2011 Elsevier B.V. All rights reserved.