In order to simply compare the performance of protective agents in the preparation of metal nanoparticles, a systematic investigation based on the same synthetic conditions is necessary. We successfully achieved this objective using improved vacuum evaporation on running oil substrate (VEROS) method. The efficient synthesis of nanoparticles with the improved VEROS method enabled us to characterize them by various analytical methods. In this study, five types of protective agents with different functional groups were employed to clarify their effect on the preparation of silver nanoparticles. They are sorbitan monooleate, oleylamine, oleic acid, oleyl alcohol, and methyl oleate. Particles synthesized by the improved VEROS method were evaluated by transmission electron microscope (TEM) and UV-vis spectrophotometer. These results indicate that sorbitan monooleate and oleic acid effectively protect the aggregation between particles. It is also evident from the evaluation of powdered nanoparticles isolated from the trap solution by thermogravimetric analysis (TGA) that these protective agents adsorb on the surface of the particles. On the other hand, the aggregates of silver nanoparticles were formed in the cases using oleic alcohol and methyl oleate. Silver nanoparticles were obtained in the case of oleylamine but the material efficiency of silver was extremely low. As a result, our systematic investigation using the improved VEROS method disclosed suitable protective agents in the preparation of silver nanoparticles with the physical method.