We report on spectroscopic study of pyrolytic hBN (pBN) by means of time- and energy-resolved photoluminescence methods. A high purity pBN samples (though low crystallinity) allow complementary information about excited states involved into the luminescence process. We affirm our recent conclusions about the impurity-related nature of most of fluorescence bands in microcrystalline hBN. In addition, a broad band centred at 3.7 eV previously not considered because of its superposition with an intense structured impurity emission is attributed to the radiative recombination of deep DAPs.