An anode catalyst layer (ACL) with novel microstructure for direct methanol fuel cells (DMFCs) based on the catalyst coated membrane (CCM) technique is prepared by heating-spray method in this paper. The morphology and pore distribution of the novel ACL are characterized by scanning electron microscopy (SEM) and specific surface area (BET) analysis, respectively. A continuous flocculent structure with abundant micropores and a clear hierarchical distribution of pore diameter are obtained in the ACL. The DMFC performance is investigated by polarization curves measurements. In compared with traditional ACL, the novel structure ACL has larger active surfaces and exhibits higher performance with 39% increase in maximum power density during the single cell test at 80 degrees C. The possible reason for the increased performance has been analyzed and ascribed to the novel structure for the ordered mass transfer and the reduced internal resistance. Crown Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.