Abstract Hydrogen evolution reaction (HER) by water splitting has made a significant contribution to producing large amounts of hydrogen gas as the next generation fuel. Development of highly efficient, economically viable, and electrochemically stable HER electrocatalysts has accordingly become a prerequisite for practical implementation of large scale water electrolysis. Mono/few-layered transition metal dichalcogenide (TMD) based HER-electrocatalysts have recently garnered great interest due to their diverse tunable electrochemical properties. However, they still face intrinsic limitations such as self-aggregation, rare active sites, high electrical resistance, and long-term electrochemical instability. To tackle these challenges, we designed and synthesized a novel electrocatalyst comprising active site-rich rhenium diselenide (ReSe2) nanoflakes perpendicularly anchored on a reduced graphene oxide (rGO) nanosheet support via a facile one-step hydrothermal synthesis. The rGO support provides a growing platform for few-layered ReSe2 nanoflakes while facilitating plentiful exposure of edge/corner sites of ReSe2, highly desirable for maximizing the catalytic activity of ReSe2@rGO. The synthesized ReSe2@rGO exhibits a low overpotential of 145.3 mV at a current density of 10 mA·cm−2 with a Tafel slope of 40.7 mV·dec−1 for the HER process due to the synergistic combination of high surface density of unsaturated coordination sites, remarkably accelerated electron transfer, and enhanced electrochemical stability. This outcome suggests using structurally regulated hybridization of TMDs and graphene as a platform toolkit for developing high performance HER catalysts.