The deposition by atomic vapor deposition of highly c-axis-oriented Aurivillius phase Bi5Ti3FeO15 (BTFO) thin films on (100) Si substrates is reported. Partially crystallized BTFO films with c-axis perpendicular to the substrate surface were first deposited at 610 °C (8% excess Bi), and subsequently annealed at 820 °C to get stoichiometric composition. After annealing, the films were highly c-axis-oriented, showing only (00l) peaks in x-ray diffraction (XRD), up to (0024). Transmission electron microscopy (TEM) confirms the BTFO film has a clear layered structure, and the bismuth oxide layer interleaves the four-block pseudoperovskite layer, indicating the n = 4 Aurivillius phase structure. Piezoresponse force microscopy measurements indicate strong in-plane piezoelectric response, consistent with the c-axis layered structure, shown by XRD and TEM.