The development of nanoscience and nanotechnology has inspired scientists to continuously explore new electrode materials for constructing an enhanced electrochemical platform for sensing. In this article, we proposed a new Pt nanoparticle (NP) ensemble-on-graphene hybrid nanosheet (PNEGHNs), a new electrode material, which was rapidly prepared through a one-step microwave-assisted heating procedure. The advantages of PNEGHNs modified glassy carbon electrode (GCE) (PNEGHNs/GCE) are illustrated from comparison with the graphenes (GNs) modified GCE for electrocatalytic and sensing applications. The electrocatalytic activities toward several organic and inorganic electroactive compounds at the PNEGHNs/GCE were investigated, all of which show a remarkable increase in electrochemical performance relative to GNs/GCE. Hydrogen peroxide (H2O2) and trinitrotoluene (TNT) were used as two representative analytes to demonstrate the sensing performance of PNEGHNs. It is found that PNEGHNs modified GCE shows a wide linear range and low detection limit for H2O2 and TNT detection. Therefore, PNEGHNs may be an attractive robust and advanced hybrid electrode material with great promise for electrochemical sensors and biosensors design.