Nanocrystalline sp²-boron nitride (BN) thin films have been grown for 2 and 4.5 h on mechanically polished polycrystalline pyrolytic boron nitride substrates at 1060 °C via chemical vapor deposition using diborane (B₂H₆) and ammonia (NH₃) as the B- and N sources, respectively. The use of an N/B gas phase ratio of 200 resulted in sp²-BN thin films having a stoichiometric surface chemistry, as determined by x-ray photoelectron spectroscopy. Cross-sectional transmission electron microscopy revealed the initial growth of ∼4 nm thick partially ordered [0001] sp²-BN layers regardless of the crystallographic orientation of the sets of layers in the substrate. A transition zone then formed within the deposited films that contained randomly oriented polycrystalline grains and that culminated in the formation of protrusions. Atomic force microscopy verified an increase in roughening of the surfaces of the films with an increase in growth time and the associated thickness.