The activity of transition metal dichalcogenides (TMD) toward hydrogen evolution reaction (HER) derives from the active sites at the edges, but the basal surface still remain catalytic insert. Herein, ultrathin MoSSe alloy nanosheets array on multiwalled carbon nanotubes (MWCNTs) to form a core shell structure via a simple solvothermal process. These three-dimensional (3D) MoSSe hybrids show a high activity in hydrogen evolution reaction (HER) with a small Tafel slope of 38 mV dec(-1) and a low overpotential of 102 mV at 10 mA cm(-2). In addition, their HER activity remains remarkably stable without significant decay after 100 h polarization. Such superior catalytic HER activity springs from the 3D hierarchical heterostructure, which is abundant of catalytic edge sites, and the alloy effect between S and Se, which will create huge defects and strain to form vacancy sites on the basal plane. This strategy may open a new avenue toward the development of nonprecious high-performance HER catalysts. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.