Structural manipulation of the two dimensional graphene surface has been of significant interest as a means of tuning the properties of the nanosheets for enhanced performance in various applications. In this report, a straightforward and highly scalable method is presented to prepare bulk quantities of “holey graphenes”, which are graphene sheets with holes ranging from a few to tens of nm in average diameter. The approach to their preparation takes advantage of the catalytic properties of silver (Ag) nanoparticles toward the air oxidation of graphitic carbon. In the procedure, Ag nanoparticles were first deposited onto the graphene sheet surface in a facile, controllable, and solvent-free process. The catalyst-loaded graphene samples were then subjected to thermal treatment in air. The graphitic carbons in contact with the Ag nanoparticles were selectively oxidized into gaseous byproducts, such as CO or CO₂, leaving holes in the graphene surface. The Ag was then removed by refluxing in diluted nitric acid to obtain the final holey graphene products. The average size of the holes on the graphene was found to correlate with the size of the Ag nanoparticles, which could be controlled by adjusting the silver precursor concentration. In addition, the temperature and time of the air oxidation step, and the catalyst removal treatment conditions were found to strongly affect the morphology of the holes. Characterization results of the holey graphene products suggested that the hole generation might have started from defect-rich regions present on the starting graphene sheets. As a result, the remaining graphitic carbon structures on the holey graphene sheets were highly crystalline, with no significant increase of the overall defect density despite the presence of structural holes. Preliminary experiments are also presented on the use of holey graphene sheets as fillers for polymeric composites. The results indicated that these sheets might be better reinforcing fillers than the starting graphene sheets due to their perforated structure. Other unique potentials of these materials, such as for energy storage applications, are also discussed.