The BaTiO3 thin film was grown epitaxially on SrTiO3(001) substrate by laser molecular beam epitaxy (laser-MBE). The film growth process w as monitored by in situ reflection high-energy electron diffraction (RHEED), the regular RHEED intensity oscillation from the 0th-Bragg reflection shows an unit cell layer-by-layer growth mode. The crystalline structure and the surface morp hology of the laser-MBE BaTiO3 film were characterized by X-ray diffr action (XRD) and by atomic force microscopy (AFM), respectively. The XRD and AFM results show that laser-MBE BaTiO3 film exhibit the tetragonal c-axi s oriented structure and an atomically smooth surface with a root mean square su rface roughness of 016nm. The topmost surface of the film was studied by angl e-resolved X-ray photoelectron spectroscopy (ARXPS), indicating the laser-MBE Ba TiO3 film is predominantly terminated with TiO2 atomic pla ne. The topmost surface of laser-ablated BaTiO3 film was also analyze d. The film growth mechanism was investigated in atomic scale.