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 determined using grazing incidence X-ray diffraction (GIXRD), its morphology imaged using the field emission scanning electron microscopy (FESEM), and its surface topography examined using the atomic force microscope (AFM) in contact mode. Cubical white spots were detected, identified as Ag, while the TiO2 thin film resembles a porous ring-like structure with each ring coalescing and forming channels. Junction growth is directly proportional with time under continuous heating conditions (annealing), and its growth orientations and patterns were seemingly random.