Capturing the surface-structural dynamics of metal electrocatalysts under certain electrochemical environments is intriguingly desired for understanding the behavior of various metal-based electrocatalysts. However, in situ monitoring of the evolution of a polycrystalline metal surface at the interface of electrode-electrolyte solutions at negative/positive potentials with high-resolution scanning tunneling microscopy (STM) is seldom. Here, we use electrochemical STM (EC-STM) for in situ monitoring of the surface evolution process of a silver electrode in both an aqueous sodium hydroxide solution and an ionic liquid of 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl) amide driven by negative potentials. We found silver underwent a surface change from a polycrystalline structure to a well-defined surface arrangement in both electrolytes. In NaOH aqueous solution, the silver surface transferred in several minutes at a turning-point potential where hydrogen adsorbed and formed mainly (111) and (100) pits. Controversially, the surface evolution in the ionic liquid was much slower than that in the aqueous solution, and cation adsorption was observed in a wide potential range. The surface evolution of silver is proposed to be linked to the surface adsorbates as well as the formation of their complexes with undercoordinated silver atoms. The results also show that cathodic annealing of polycrystalline silver is a cheap, easy, and reliable way to obtain quasi-ordered crystal surfaces.