Highly ordered Ag films grown on cleaved mica with a two-step procedure were characterized in detail with several techniques for surface analysis, including low-energy electron diffraction, X-ray photoemission spectra, a scanning tunneling microscope and angle-resolved photoemission spectra. Silver films of a thickness ≥ 100 nm were deposited on mica substrates at 300 K and stored under ambient conditions. The Ag/mica films became atomically flat and free of contamination when they were transferred into ultra-high vacuum and prepared with sputtering and annealing. The experimental results indicate that the surfaces of the cleaned Ag/mica films have structural and electronic properties resembling those of a Ag(111) single crystal with ordered domains aligned over a macroscopic region, but the surfaces of the Ag/mica films became rough on annealing above 623 K. On the rough surfaces, the surface steps tended to bunch together, yielding flat terraces bound with steps of large heights. With the decreased thermal stability in mind, the Ag/mica film is adoptable as a cheap platform alternative to a Ag(111) single crystal for the growth of highly ordered overlayers.