A P, N dual-doped holey graphene (PNHG) material is prepared by a scalable, facile synthetic approach, using a mixture of glucose, dicyandiamide (DCDA), and phosphoric acid (H3PO4). H3PO4 successfully functions as an "acid catalyst" to encourage the uniform breakage of C = C bonds to create large, localized perforations over the graphene monolith. Further acid treatment and annealing introduce in-plane holes. The correlation between the capacitance of the PNHG and its structural parameters during the fabrication process is comprehensively evaluated. A thermally induced sp(2)-> sp(3) transformation occurs at high temperatures because of the substantialloss of graphitic sp(2)-type carbons, together with a dramatic reduction in capacitance. The target PNHG-400 electrode material delivers exceptionally high gravimetric capacitance (235.5 F g(-1) at 0.5 A g(-1)), remarkable rate capability (84.8% at 70 A g(-1)), superior capacitance retention (93.2 and 92.7% at 10 and 50 A g(-1) over 25000 cycles, respectively), and acceptable volumetric capacitance due to moderate density, when it is used with organic electrolytes in the voltage range between 0 and 3 V. These results suggest a pioneering defect-engineered strategy to fabricate dual-doped holey graphene with valuable structural properties for high-performance electric double layer supercapacitors, which could be used in next-generation energy storage applications.