One dimensional boron nitride (BN) nanomaterials with a high aspect ratio are of great interest due to their unique properties and potential applications. However, BN nanomaterials are generally difficult to synthesize. Here, we describe the creation of arrays of vertically aligned pure BN nanofibers and BN coated carbon nanofibers, fabricated on-chip via a straightforward template-assisted chemical conversion reaction. The template, a glassy carbon nanofiber array, is produced by plasma processing of conventional photoresists. The method is highly controllable, patternable, and scalable, and the final arrays can be fabricated over large areas with a controlled fiber length. We characterize the electron field emission properties of the BN-coated carbon nanofiber array and find a large field enhancement factor, low turn-on voltage, and good stability. The outstanding field emission performance results from the small tip size and high aspect ratio of the nanofiber as well as the high chemical stability and high thermal conductivity of the BN coating.