The influence of mercury on the morphology and formation mechanism of gold amalgams in the presence of different reducing agents (ascorbic acid and sodium borohydride) was systematically studied. In the presence of cetyltrimethylammonium bromide (CTAB), chemical reducing agents not only reduced mercury ions in the solution but also replaced the CTAB molecules on the surface of the gold nanorod. The stability of the reducing agents in the colloidal system and the combining capacity of the reducing agent to the gold nanoparticles can affect the alloying process of mercury and gold, thereby forming a rod-shaped or spherical gold amalgam. Once CTAB was removed, a similar transformation process occurs between the gold nanorods and mercury. In addition, without the presence of a stabilizer, mercury that cannot be dispersed undergoes Ostwald ripening growth, which causes the gold amalgam nanoalloys to form a tip-to-tip structure as a result of mercury enrichment because of the weak shielding effects occurring at the tips of the gold nanorods. After the CTAB molecules were substituted with ascorbic acid and alkylthiol molecules, the question of whether the shielding effect weakened or disappeared was also investigated. By investigation, this research found that, in comparison to the blocking effect of CTAB molecules, the binding ability of the reducing agent to gold plays a dominant role in the nanoamalgam formation process.