The development of metal-free catalyst for oxygen reduction reaction (ORR) is one of the most challenging tasks in fuel cells. Heteroatom doped graphenes have been recognized as the promising candidate. In this work, we have developed a one-pot hydrothermal approach towards three-dimensional nitrogen and sulfur co-doped graphene frameworks (N/S-GFs) employing graphene oxide and ammonium thiocyanate as the precursors. N/S-GFs manifest excellent catalytic behavior with mainly four electron transfer pathway in ORR in alkaline condition.