Multi-walled carbon nanotube (MWCNT) multilayer thin films with controlled thickness were preassembled on electrodes by alternatively depositing MWCNT and poly(diallyldimethylammonium chloride) (PDDA) via a layer-by-layer self-assembly technique. Silver nanoparticles (Ag NPs) were then electro-deposited on the MWCNT surface from AgNO3 solution using a potentiostatic double pulse technique. The size, density and morphology of silver nanoparticles that electrodeposited on MWCNT were controlled by the pulse parameters. When a voltage pulse of -600 mV was used to nucleate silver nanoparticles and a growth pulse of -105 mV was applied to grow the particles, silver particles of 10-500 nm with varied density could be electro-generated on MWCNT surface. The formation of Ag NPs and the morphology of the MWCNT/Ag NP composite films were characterized by scanning electron microscopy (SEM). The MWCNT/Ag NP composite films exhibited excellent electrocatalytic activity to the reduction of hydrogen peroxide which was also shown to be slightly affected by the size and density of Ag NPs on the film. (C) 2012 Elsevier Ltd. All rights reserved.