Herein, we report a facile and novel strategy for the synthesis of 3-dimensional holey graphene nanoarchitecture, which is appropriately functionalized with nitrogen and sulfur via hydrothermal-assisted chemical etching of graphene oxide using ammonium persulfate. The chemical functionalization of the material was proved from XPS and FTIR spectral analyses. Sulfur exists as sulfonic acid group, whereas nitrogen got doped into the graphene network as revealed from the XPS analysis. The 3-dimensional morphology as well as porous nature of the developed material was confirmed from SEM and TEM images, respectively. Raman spectral analysis indicated the defective nature of the holey graphene as expected. Both N doping and sulfonation could enhance the utility of holey graphene as a carbocatalyst when compared to graphene oxide or reduced graphene oxide. The prepared material showed high catalytic efficiency towards the selective oxidation of ethylbenzene to acetophenone.