In this work, we designed various polyaniline (PANI) nanocomposites with platinum (Pt) nanoparticle-decorated multi-walled carbon nanotubes (MWCNTs), employed them as anodic catalysts, and studied their structural assembly effects with regard to enhancing biohydrogen fuel cell performance. Of two proposed structures, the PANI/Pt/MWCNTs multilayer nanocomposites showed superior electrocatalytic activities in the hydrogen oxidation reaction and in fuel cell power density relative to the Pt/MWCNTs@PANI core-shell design. These enhancements were attributed to the active interface formed between the Pt nanoparticles and polyaniline nanofibers, where the higher electronic and ionic conductivities of the thin PANI nanofiber layers in contact with Pt active sites were better than with the PANI bound Pt/MWCNTs. We also investigated the change in the electronic state of the composites and the charge-transfer rate caused by varying the structural assembly. Finally, the role of each catalyst component was examined to understand its individual effect on fuel cell performance and to understand its structural assembly effect on enhanced power density. (C) 2011 Elsevier Ltd. All rights reserved.