Absorption and scattering properties of pyrolytic boron nitride (pBN) have been characterized by infrared spectroscopy. The strong dielectric anisotropy predicted by first principles calculations is confirmed by measurements performed on a highly oriented pBN sample. Optical properties of textured samples elaborated by chemical vapor deposition were identified from normal hemispherical reflectance and transmittance spectra by applying modified two-flux and four-flux transport models. It is also shown that coating carbon–carbon composites used to build solar shields with a pBN layer having an optimal thickness could improve the protection performance.