There is great interest in BiFeO 3 and various substituted heterostructures for ferroelectric random-access memory (RAM) and energy-efficient magnetoelectric logic and memory devices. High-quality heterostructures of these material systems with smooth topography are desirable to incorporate into functional devices. For this purpose, the direct liquid injection chemical vapor deposition (DLI-CVD) technique has been employed to grow BiFeO 3 and Bi-site samarium-substituted epitaxial films on (001)-oriented SrTiO 3 and SrRuO 3 -buffered SrTiO 3 substrates. Structural and morphological characterizations of the films are carried out using X-ray diffraction, atomic force microscopy, and scanning electron microscopy techniques. The films show textured growth and exhibit smooth morphology with root mean square roughness below 2.5 nm. Ferroelectric characteristics and memory retention in thin films are demonstrated using piezoresponse force microscopy. The thickness scaling of the switching voltage has been analyzed to validate the Kay−Dunn law for Sm-substituted BiFeO 3 and compared with that of pure BiFeO 3 .