A novel electrochemical sensing platform was constructed based on a facile self-assembly procedure synthetic laminar molybdenum trioxide dihydrate (MoO[Formula: see text]H2O)-graphene composite. Field emission scanning electron microscopy (FESEM), X-ray spectroscopy, X-ray diffraction (XRD) and Raman spectroscopy were employed to characterize the morphology and composition of the MoO[Formula: see text]H2O-graphene composite. As a model molecule, thiourea was utilized to investigate the electrochemical behaviors of the MoO[Formula: see text]H2O-graphene composite modified glass carbon electrode. The results show that the composite modified electrode has higher electron transfer rate than that of graphene modified electrode and bare glass carbon electrode meanwhile the peak currents of it has a good linear relationship with thiourea concentrations in the range of [Formula: see text] ([Formula: see text]) with detection limit of 4.99[Formula: see text][Formula: see text]M ([Formula: see text]). This novel electrochemical sensor exhibits a higher absorption capacity ([Formula: see text][Formula: see text]mol/cm2), a good reproducibility (1.41% relative standard deviation (RSD)), excellent anti-interference and a high stability. These excellent electrochemical properties of the MoO[Formula: see text]H2O-graphene composite are attributed to the loose and porous structure and the synergistic effects between graphene and MoO[Formula: see text]H2O, which make this composite material hold great potential applications for electrochemical sensor.