The electrochemical detection of hydrogen peroxide (H2O2) has attracted much attention recently. Meanwhile, the size of nanoparticles which significantly influences electrocatalytic activity is crucial for electrocatalysts. Hence, we prepared five different size-selected Pt/graphene-modified glassy carbon (GC) electrodes to characterize H2O2 level via electrochemical measurements. During the preparation of the nanocomposites, size-selected Pt nanoparticles (NPs) with the mean diameter of 1.3, 1.7, 2.9, and 4.3 nm were assembled onto the graphene surfaces. The electrochemical measurement results are size-dependent for Pt NPs when sensing H2O2. When all cyclic voltammogram results from various electrodes are compared, the Pt-1.7 nm/G-modified GC electrode has the highest reduction current, the best detection limit, and the best sensitivity.