Boron nitride containing titanium nitride in an amount of 0.05 to 10 wt. % which is produced at a relatively low temperature, utilizing a chemical vapor deposition technique. In the deposition process, boron, titanium and nitrogen source gases are introduced into an evacuated reactor together with a carrier and/or diluent gas and contacted with a heated substrate previously mounted in the reactor, whereby boron nitride with titanium nitride is deposited onto the substrate. The deposit thus obtained has a high density, a significantly improved heat-shielding ability, a high degree of anisotropy with respect to thermal diffusivity and a high chemical stability. By using such anisotropic boron nitride with BN ceramics, very useful BN type composite ceramics can be produced.