The defect sites on chemical vapor deposition grown graphene are investigated through the selective electrochemical deposition (SED) of Au nanoparticles. For SED of Au nanoparticles, an engineered potential pulse is applied to the working electrode versus the reference electrode, thereby highlighting the defect sites, which are more reactive relative to the pristine surface. Most defect sites decorated by Au nanoparticles are situated along the Cu grain boundaries, implying that the origin of the defects lies in the synthesis of uneven graphene layers on the rough Cu surface.