AbstractGraphite responds to nitro addition by NO2 radical and the nitro derivative isomerizes to energetically favorable nirito form under ambient condition. This derivative readily hydrolyzed in forming poly‐hydroxylated graphene, “graphenol”. The (graph)‐enol responds to irreversible transformation in its keto form with 1,4 hydrogen shift yielding the graphene oxide (GO) as the end product that also possesses C−H bonds. The conventional methodology used in synthesizing GO under strong acid medium inherently follow this NO2 and similar sigma centric free radical addition reactions. These energy released reactions are supported by density functional theoretical (DFT) calculation.