This work focuses on a simplified polyol process by which to synthesize five different NiCu/C nanoclusters (NCs) electrocatalysts with the variation of mass and atomic ratio. NCs are characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, transmission electron spectroscopy (TEM), and scanning electron microscopy with energy-dispersive spectroscopy (EDS) for their crystallite and electronic structures, morphological studies, and elemental composition. The high-angle annular dark-field scanning TEM coupled with EDS elemental mapping has confirmed that nanoparticles (NPs) are formed with Ni and Cu, and NPs are subsequently noted to conform into NCs in such a fashion that NiCu NPs are interconnected to each other rather than overlapping considered a unique distribution of NiCu NCs on the carbon support observed in STEM. NPs arrangement in the conformation of NCs has largely increased in the coverage of NiCu-oxyhydroxides working as active sites for ammonia electrocatalysis evidenced in cyclic voltammograms and XPS investigation. NCs were employed for the oxidation of NH4OH, NH4Cl, NH4NO3, and (NH4)2SO4 of which NiCu/C-2 has shown the highest performance over other NiCu/C samples and their individuals. NiCu/C-2 is also found to have higher stability than other mono/bi-metallic electrocatalysts on the stability test preformed in an electrochemical environment. In addition, the sharp drops of the current in the chronoamperometric curves have been investigated during the stability test.