This review reports on catalytic activity, for some relevant organic reactions, of graphene oxide (GO) and of high‐surface‐area graphite (HSAG). It is shown that main drawbacks of graphite‐based catalysts, i.e. high catalyst loading and generally poor selectivity, can be often removed, by operating in solvent‐free conditions. Moreover, some reactions, which are catalyzed by GO as well as by HSAG, are presented. For these reactions, π stacking of aromatic substrates with graphitic planes has a predominant role for the catalytic activity as well as for unexpected diastereoselective and enantioselective behaviors.