This article presents investigation of syntheses of perovskite PbTiO3 thin films by using reactive magnetron layer-by-layer deposition on Si (100) substrate and post-annealing in air and vacuum (p = 5 × 10 −3 Pa). The film stoichiometry was accurately controlled by the deposition of individual layers with the required (≈ 1 nm) thickness, using the substrate periodic moving over targets. Deposited thin films were annealed in air and in vacuum at 670• C and 770• C for 1 h, respectively. The morphological, structural, and chemical properties of thin films deposited at 300• C substrate temperature and post-annealed thin films using either conventional annealing and thermal annealing in vacuum at different temperatures were investigated and compared between. X-ray diffraction measurements of thin films annealed in air show formed crystalline perovskite PbTiO3 phase with tetragonality c/a = 1.047. The crystallite size of oxidized films depends on the substrate temperature. The structure of post annealed in vacuum thin films strongly depends on Pb/Ti atomic ratio. It was observed that the best structure and morphology forms when atomic ratio of Pb/Ti was 0.80. Pseudocubic phase of lead titanate forms with sufficiently low tetragonality at 670• C temperature.