A rational design of electrode materials with both high electron conductivity and abundant of catalytic sites is essential for high-performance electrochemical reactions. Herein, a nitrogen and sulfur co-doped graphene (SNG) anchored on the interconnected conductive graphite foam (GF) is fabricated via drop-casting and in situ annealing. The SNG flakes are tightly immobilized on the GF surface, which can provide fast electron transfer rate and large electrolyte/electrode interfaces. The SNG@GF composite can be directly used as a free-standing electrode for electrocatalytic degradation of organic pollutants and overall water splitting. SNG@GF significantly enhanced the electrochemical activation of peroxymonosulfate (PMS) for catalytic oxidation. During the oxygen evolution reaction (OER), the SNG@GF exhibits an initial overpotential of 330 mV vs. RHE at 10 mA cm(-2) with a Tafel slope of 149 mV dec(-1) in 1 M KOH, which outperforms most of the reported metal-free catalysts. The density functional theory calculations are also used to unveil the S, N dual doping effects of carbon materials and their synergy in carbocatalysis. This study dedicates to developing multi-functional carbocatalysts for environmental and energy applications, and enables insights into carbocatalysis in electrochemistry. (C) 2020 Elsevier Inc. All rights reserved.