Boron nitride (BN) films with a wide variety of nano-network structures (sp2–sp3 bonded) were prepared and their sputtering behaviors were investigated. BN films were formed using a reactive plasma-assisted coating technique. Fourier transform infrared spectroscopy (FT-IR) and nanoindentation analyses confirmed the presence of sp2- and sp3-bonded phases. Then, the thickness change by plasma exposure was studied for various BN films. Sputtered depth after the plasma exposure of the prepared BN films was lower than that of SiO2 films. While no clear change was observed in the FT-IR spectra after the plasma exposure, the leakage current and dielectric constant changed due to the surface modification. It was found that the modified layer underneath the sputtered surface contained the local defects which play a role as carrier trapping or hopping sites. The sputtering behavior analysis in combination with electrical measurements is a useful methodology for designing BN films.