Highly active metal-free electrocatalysts consisting of earth-abundant elements for oxygen evolution reaction (OER) are extremely desired for renewable energy technologies. Here we prepare the nitrogen and sulfur co-doped graphene/carbon nanotube (NS-GR/CNT) with 3D architecture by one-step hydrothermal method, which presents good performance for OER. The as -prepared NS-GR/CNT exhibits more negative onset potential and lower Tafel slope (0.56 V, 103 mV decade (1) vs. S.C.E. in 0.1 M KOH) compared to single N doped graphene/carbon nanotube (0.65 V, 285 mV decade 1), which indicates S doping can significantly enhance the OER performance. The X-ray photoelectron spectroscopy reveals that the thiophene-like S (C-S-C) is the dominant S species in all the S doped samples. NS-GR/CNT with C-S-C content of 0.26% has the Tafel slope of 151 mV decade 1 while the value for NS-GR/CNT with C-S-C content of 1.09% is 103 mV decade (1). The decreased Tafel slope demonstrates the catalytic kinetics are highly correlated with the content of C-S-C. Density functional theory calculations suggest that C-S-C may improve the catalytic kinetics by facilitating the adsorption of the OH intermediate. Besides, the 3D architecture composed of graphene and CNTs also contributes to the good performance and chronoamperometric measurement demonstrates the good durability of NS-GR/CNTs. (C) 2016 Elsevier Ltd. All rights reserved.