The state-of-the-art density functional theory (DFT) is employed to study the catalytic activity of arsenene for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). We have included dispersion correction to get accurate adsorption energy on the individual catalytic surface (top site). Using binding energy calculation, arsenene is shown to be a potential candidate for HER. Here we investigate the stability and electronic properties of the honeycomb structure of the arsenene system using first-principles calculation to find the effect of different dopants on the fundamental band gap, which is one of the primary parameters in the photocatalytic water splitting. Further, we sieved the dopant for better HER catalytic activity by substituting one of the arsenene (As) atoms by B, N, O, Ge, Ga and Se atoms to make arsenene a better candidate for HER. Our studies depict that HER activity is increased by 82% for O-doped arsenene and OER activity by 87% for B-doped arsenene as compared to pristine arsenene. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.