MoS2, a two-dimensional nanomaterial analogous to graphene, has interesting catalytic properties that make it suitable for the hydrogen evolution reaction, but reports are scarce on its fuel cell application. Herein, we report a novel vertically aligned crumpled MoS2nanosheet hybrid nanostructure architecture on porous Ni foam (MoS2/NF-5) via a facile, one-pot hydrothermal synthesis approach. The porous binder-free Ni foam (NF) promotes the uniform growth of ultrathin MoS2nanosheets, due to its grain boundaries acting as nucleation sites, and reduces the interfacial resistance between MoS2and substrate. The hybrid nanostructure of spongy nanoparticles decorated over nanosheets morphology provides synergistic effect for rapid charge transfer reaction with short diffusion path and enhances the electrocatalytic active sites. The electrochemical analysis of as-obtained optimized MoS2/NF-5 reveals an outstandingly high electroactive surface area with the presence of both adsorption and diffusion process at the surface, indicating its potential toward a variety of electrochemical applications. The binder-free MoS2/NF-5 displays excellent electro-oxidation of methanol with high current tolerance of 73 mA/cm2, high durability (only 20% loss after 5000 s), and low overpotential (0.3 V) due to the presence of electroactive sites and conductive substrate for facile charge transportation. Hence, this platform of MoS2morphology directly grown on 3D NF substrate with excellent electrochemical properties can be utilized as a potential binder-free electrode for catalytic and electrochemical applications. © 2021 American Chemical Society