Abstract: Barium strontium titanate (Ba_0.5Sr_0.5TiO₃, BST)/silicon nanoporous pillar array (Si-NPA) thin films were prepared by a spin-coating/annealing technique based on Si-NPA with micro/nano-structure. Both the isomer conversion of acetylacetone and the network structure combined by enol and Ti-alkoxide facilitate the formation of the BST sol and the subsequent crystallization. Before the perovskite BST begins to form, the intermediate phase (Ba,Sr)Ti₂O₅CO₃ is found. The boundary between BST and Si-NPA is of clarity and little interface diffusion, disclosing that Si-NPA is an ideal template substrate in the preparation of multifunctional composite films.