The development of efficient electrocatalysts for hydrogen generation is an essential task to meet future energy demand. In recent years, molybdenum ditelluride (MoTe2) has triggered incredible research interests due to intrinsic nontrivial band gap with promising semi-metallic behaviors. In this work, 2D MoTe2 nanosheets have been synthesized uniformly on graphene substrate through ultra-fast microwave-initiated approach, that shows a superior hydrogen evolution in acidic medium with low overpotential (similar to 150 mV), low activation energy (8.4362 +/- 1.5413 kJ mol(-1)), along with a Tafel slope of 94.5 mV/decade. Interestingly, MoTe2/graphene exhibits the enhanced electrocatalytic stability during the long cycling test, resulting an increase in specific surface area of catalyst materials. Moreover, the results from periodic plane-wave density functional theory (DFT) indicate that, the best active sites are the corner of a Mo-atom and a critical bifunctional site comprised of adjacent Mo and Te edge atoms. Furthermore, the corresponding volcano plot reveals the near thermoneutral catalytic activity of MoTe2/graphene for hydrogen generation. (C) 2020 Elsevier Inc. All rights reserved.