Ag/TiO2 thin films were prepared using the sol-gel spin coating method. The microstructural growth behaviors of the prepared Ag/TiO2 thin films were elucidated using real-time synchrotron radiation imaging, its structure was determined using grazing incidence X-ray diffraction (GIXRD), its morphology was imaged using the field emission scanning electron microscopy (FESEM), and its surface topography was examined using the atomic force microscope (AFM) in contact mode. The cubical shape was detected and identified as Ag, while the anatase, TiO2 thin film resembled a porous ring-like structure. It was found that each ring that coalesced and formed channels occurred at a low annealing temperature of 280 °C. The energy dispersive X-ray (EDX) result revealed a small amount of Ag presence in the Ag/TiO2 thin films. From the in-situ synchrotron radiation imaging, it was observed that as the annealing time increased, the growth of Ag/TiO2 also increased in terms of area and the number of junctions. The growth rate of Ag/TiO2 at 600 s was 47.26 µm2/s, and after 1200 s it decreased to 11.50 µm2/s and 11.55 µm2/s at 1800 s. Prolonged annealing will further decrease the growth rate to 5.94 µm2/s, 4.12 µm2/s and 4.86 µm2/s at 2400 s, 3000 s and 3600 s, respectively.