In the present study we focus on the interaction of C60 with sp2 boron nitride (BN), a surface that is isoelectronic to graphite. The nanocrystalline BN substrate was deposited by mass selected ion beam and consists of an sp2 surface layer, which covers a cubic-BN film. The interaction and electronic properties of the C60-BN system are observed by photoelectron spectroscopy in the x-ray (XPS) and ultraviolet regime (UPS). The experiment is initiated by sequential deposition of C60 and the overlayer growth proceeds via island formation. In a second step the sample is annealed at a rate of 5–10 K/minute while simultaneously recording the UPS spectra. The majority of C60 desorbs from the sp2 BN surface at 493 K. The remaining C60 (initially about 0.6 ML) is gradually removed with increasing temperature (up to 813 K) but never completely desorbed and presumably attached at surface imperfections or grain boundaries of the nanocrystalline material. No carbide formation, preferential interaction of C60 with either element or a charge transfer are observed. The presence of C60 induces an upward band bending and related peak shifts in the sp2 BN surface layer and to a lesser extent in the underlying c-BN bulk. An upward band bending is likewise observed in the C60 overlayer, and the Fermi level has therefore to be pinned by defects in the interface region. The layered structure of the BN film allows to probe the extension of the space charge layer in the BN film.