Three-dimensional (3D) structured Pt/C/graphene aerogel (Pt/C/GA) hybrid as a remarkable high stability electrocatalyst is synthesized through a facile and green hydrothermal process. Thanks to the unique 3D graphene framework structure, Pt/C/GA hybrid catalyst demonstrated enhanced stability towards methanol electrooxidation with no decrease of electrocatalytic activity. Besides, Pt/C/GA hybrid catalyst also exhibits a significantly enhanced stability to scavenge crossover methanol under the high potential in acid solution compared with the standard Pt/C catalyst: Pt/C catalyst lost nearly 40% of its initial activity after 1000 cyclic voltammetry cycles, by contrast, only 16% for Pt/C/GA. Moreover, it is noteworthy that after 200 cycles, the mass activity of Pt/C/GA is always much higher than that of Pt/C. A significant stability enhancement is achieved due to the unique 3D macroporous graphene structure as well as the efficient assembly between the Pt/C catalyst and graphene aerogel. Importantly, our synthetic strategy can be easily applied to the commercial PtRu/C catalyst to improve its durability. This simple, convenient and green synthetic method highlights the potential in fabrication of high durable electrocatalyst for fuel cell applications.