Nickel (Ni) nanoparticles (NPs) prepared through vapor-phase synthesis (VPS) are preferred for multilayer ceramic capacitor electrodes due to their high purity and crystallinity advantages. Agglomerated Ni NPs are usually generated using VPS but are undesirable because they cause various problems such as low packing density and electrical shorts. This study proposes the use of coating-assisted chemical vapor synthesis (CVS) for agglomerate inhibition using NaCl or KCl as a coating agent. We have found that the agglomeration ratio, 34.40%, for conventional CVS, can be reduced to 4.80% in the proposed method by in-flight coating with KCl at 900 °C by image analysis using field-emission scanning electron microscopy. Furthermore, the X-ray diffraction and X-ray fluorescence analyses confirm that the NaCl and KCl coating agent can be removed by washing with distilled water. We believe that this coating process can be used to inhibit the formation of agglomerates during the CVS of Ni NPs.