Integration of highly anisotropic multiferroic thin films on silicon substrates is a critical step towards low-cost devices, especially high-speed and low-power consumption memories. In this work, an oxide–metal vertically aligned nanocomposite (VAN) platform has been used to successfully demonstrate self-assembled multiferroic BaTiO₃–Fe (BTO–Fe) nanocomposite films with high structural anisotropy on Si substrates. The effects of various buffer layers on the crystallinity, microstructure, and physical properties of the BTO–Fe films have been explored. With an appropriate buffer layer design, e.g. SrTiO₃/TiN bilayer buffer, the epitaxial quality of the BTO matrix and the anisotropy of the Fe nanopillars can be improved greatly, which in turn enhances the physical properties, including the ferromagnetic, ferroelectric, and optical response of the BTO–Fe thin films. This unique combination of properties integrated on Si offers a promising approach in the design of multifunctional nanocomposites for Si-based memories and optical devices.