Ba–Ti–O films were prepared on Pt-coated Si substrate by laser chemical vapor deposition, and their orientations and microstructures were compared. Ba 2 TiO 4 , BaTiO 3 , BaTi 2 O 5 , Ba 4 Ti 13 O 30 and BaTi 4 O 9 single-phase films were prepared at Ti to Ba molar ratio from 0.41 to 3.49. The α′-Ba 2 TiO 4 film showed (010) and (091) co-orientation with elongated, truncated columnar grains. The BaTiO 3 film was composed of triangular and hexagonal grains with slight (111) orientation. The BaTi 2 O 5 film had (010) orientation and faceted columnar grains. The Ba 4 Ti 13 O 40 film showed (100) and (012) co-orientation with shellfish-like grains. The BaTi 4 O 9 film showed (010) orientation with slightly rounded faceted columnar grains. The deposition rates of Ba–Ti–O films ranged from 30 to 144μmh −1 .