Local control in microstructure in nanocrystalline solid materials emerges from their property and reactivity. Similar observation is also seen for nanostructured glassy alloys accounting for enhanced properties of nanoglass compared to their metallic glass analogue. Here, we show synthesis and detailed microstructural characterization of a Ni 60 Nb 40 nanoglass starting from amorphous nanoparticles and compared the results with a melt-spun ribbon (MSR) of identical atomic composition. The effect on the magnetic property during the consolidation of glassy nanoparticles at different uniaxial pressures to create such nanoglass is studied in detail. While nanoglass showed ferromagnetic behavior at every compaction pressure, the MSR always remained paramagnetic although its density was comparable. Not only that the amorphous phase of these two materials behaves differently, when annealed above their crystallization temperature, annealed nanoglass responded distinctly differently compared to the MSR confirming non-identical local structure even after heat treatment. Taking advantage of the presence of amorphous nickel, the enhanced response of the glassy interface in the nanoglass, we tested these materials for the electrochemical methanol oxidation reaction (MOR) in alkaline medium and found that the nanoglass offers reasonably high MOR capacity compared to the MSR. The structure−property correlation in the context of energy application using such nanoglass materials is tested for the first time.