Recent developments in graphene related materials including molybdenum disulfide (MoS2) is gaining popularity as efficient and cost-effective nanoscale electrocatalyst essential for hydrogen production. These “clean” energy technologies require delicate control over geometric, morphological, chemical and electronic structure affecting physical and electrochemical catalytic properties. In this work, we prepared three-dimensional hierarchical mesoporous aerogels consisting of two-dimensional functionalized graphene and MoS2 nanosheets of varying ratio of components under hydrothermal–solvothermal conditions (P T 2, highcurrent density, and good stability was achieved with desulfurization. These results are compared with continuous multilayer MoS2 films highlighting the multiple role of tunable structure and electronic properties. The adjacent S-vacancy defectsinduced increase in density of states, dissociation and confinement of water molecules at the pore edge and planar S-vacancy sites calculated using density functional theory helped in establishing improved heterogeneous electrocatalytic rate. This is supported with combined measurements of diffusion coefficient and heterogeneous electron transfer rate via surface-sensitive scanning electrochemical microscopy (SECM) technique.