• Integration of Ru nanoparticles and Ni-V 2 NO heterostructures via electrospinning. • Electronic donation of Ni-V 2 NO to tune the electronic structure of Ru. • The introduction of Ni-V 2 NO can generate numerous accessible active sites. • Noticeably enhanced HER activity caused by the interaction between Ru and Ni-V 2 NO. Herein, we have successfully synthesized a non-Pt electrocatalyst in form of Ru nanoparticles decorated Ni-V 2 NO heterostructures in carbon nanofibers (Ru/Ni-V 2 NO/NCNFs) through annealing electrospun produced Ru-Ni 3 V 2 O 8 -PAN nanofibers under Ar atmosphere. The integration of Ru nanoparticles and Ni-V 2 NO heterostructures can regulate the electronic structure of Ru by the interaction among active components and thereby benefit the improvement of HER performance. Meanwhile, enormously boosted ECSA can be detected as the introduction of Ni-V 2 NO heterostructures, which reveals the favorable exposure of active sites. Thus, compared to the samples solo modified by Ru or Ni-V 2 NO, the as-fabricated Ru/Ni-V 2 NO/NCNFs has shown distinctly improved HER performance delivering an overpotential of merely 74.5 mV at 10 mA cm −2 with Tafel slope of 60.7 mV/dec and long-term stability in alkaline solution. It is believed that our work can provide reasonable inspirations for the design of novel non-Pt heterostructured electrocatalysts used in hydrogen generation via electrochemical water splitting.