Ba0.65Sr0.35TiO3 (BST) thin films have been fabricated on silicon field emitter arrays (FEAs) using sol-gel coating for electron emission applications. The BSTcoatings exhibit the perovskite structure when annealed between 650 and 700 degrees C, and an interfacial reaction occurs when annealed above 750 degrees C The threshold electric field is lowered from 36 V/mu m for bare silicon tips to 19 V/mu m for BST-coated silicon tips. The oxygen vacancy concentration increases for BST thin films annealed from 600 to 750 degrees C, and decreases above 750 degrees C, leading to the Fermi energy shift. The electron emission behavior is correlated to both the microstructure and electronic structure of the BST thin films.