Exploration of high-efficiency Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is considered as a great challenge for the development of sustainable and carbon dioxide free energy conversion systems. In this work, a unique hierarchical nanostructure of few-layered MoSe₂ nanosheets perpendicularly grown on carbon nanotubes (CNTs) is synthesized through a one-step solvothermal reaction. This rationally designed architecture based on a highly conductive CNT substrate possesses fully exposed active edges and open structures for fast ion/electron transfer, thus leading to remarkable HER activity with a low onset potential of −0.07 V vs. RHE (reversible hydrogen electrode), a small Tafel slope of 58 mV per decade and excellent long-cycle stability. Therefore, this noble-metal-free and highly efficient catalyst enables prospective applications for industrial, renewable hydrogen production.