Graphene based materials are considered as promising catalysts towards electro-catalytic water splitting. Heteroatoms doping and structure defects creation in graphene matrix could enhance the electrocatalytic activity effectively. In this work, a nitrogen and sulfur co-doped graphene is synthesized and then activated by KOH to involve a porous structure. The atomic ratios of doped heteroatoms are found increased surprisingly. This should be due to the better thermal stability of doped heteroatoms compared with the origin carbon atoms. More carbon atoms will be removed, thus leading to the increased heteroatoms doping percentages. The increased surface area, larger heteroatoms ratios, and abundant structure defects result in the improved catalytic activity towards electrochemical oxygen evolution reaction (OER). The overpotential for OER could achieve as early as 281 mV vs. RHE at 10 mA.cm(-2) in 1 M KOH, better than most of the metal free catalysts. The obtained sample is active over a wide pH range in electrochemical hydrogen evolution reaction (HER), thus could be used as bifunctional materials for water splitting. This work provides a simple and low-cost approach to increase the ratios of doped heteroatoms, and thus should have great potential both for carbon materials synthesis and hydrogen production. (C) 2020 Elsevier Inc. All rights reserved.