A simple approach to develop a single layer graphene decorated with rhodium nanoparticles (RhNPs) on a flexible polyethylene terephthalate (PET) substrate is presented. The ability to control the distribution and size of the RhNPs on the CVD graphene support upon changing the electrodeposition conditions is demonstrated. The distribution of the RhNPs Systematically increased with increasing of the electrodeposition time. The electrodeposition mechanism of rhodium on graphene substrates was also investigated by compared with theoretical curves for 3D progressive and instantaneous nucleation. The successful formation of the Rh decorated graphene was confirmed by scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The greatly enhanced electrocatalytic activity of the RhNPs-CVD graphene surfaces has been illustrated in connection to voltammetric and chronoamperometric measurements of hydrogen peroxide. Such CVD graphene decorated with RhNPs allows for high mass transport access and catalytic activity which provide high sensitivity and low detection limit. Based on its electrochemical enhancement, the RhNPs-CVD graphene assembly offers a promising sensing platform for next-generation flexible sensors for hydrogen peroxide or biosensors applications. (C) 2017 Published by Elsevier B.V.