The development of composite membranes and catalyst containing membranes (CCMs) with low methanol permittivity attracts a great deal of research attention for achieving higher performance in direct methanol fuel cells (DMFCs). Here, the fabrication and DMFC performance of composite and catalyst containing membranes (CCM) via layer-by-layer (lbl) technique are demonstrated. lbl composite and catalyst containing membrane based membrane-electrode assemblies (MEAs) show quite impressive cell performance. While the single cell performances of lbl composite membrane based MEAs are found to be in the range of 19.5 and 22 mW cm(-2), DMFC performance of MEA obtained from Pt containing self-assembled 10 bilayer of polyallylamine hydrochloride and polyvinylsulfonic acid, (PAH/PVS-H+)(10-pt), is found to be 24 mW cm(-2). This performance is nearly 65.5% higher compared to pure Nafion((R)) 112 based MEA. Inductive coupling plasma-mass spectroscopy (ICP-MS) result shows that Pt particles incorporate inside lbl multilayers with a loading of 0.28 mu gcm(-2). From the analyses of the performance evaluations, it is emphasized that the use of thin lbl catalyst containing membranes can be possible and quite promising in DMFC applications instead of thicker membranes due to their improved methanol barrier properties as well as proton conductivity. (c) 2013 Elsevier Ltd. All rights reserved.