Synthesis of crystalline biotite-mica thin films was examined by applying a two-step process: (1) low-temperature growth of the mica film precursor on an ultrasmooth sapphire (α-Al2O3 single crystal) substrate by pulsed laser deposition using a sintered biotite ceramics target and (2) post-annealing in vacuum. X-ray diffraction and Raman scattering spectroscopy confirmed that a c-axis-oriented polycrystalline biotite-mica thin film was obtained by post-annealing the 500 °C-grown film precursor at temperatures above 700 °C in vacuum. An atomic-scale pattern corresponding to that of the cleaved natural mica surface was observed on the surface of thin film by atomic force spectroscopy.