Here, a facile dual templates method for the synthesis of hierarchical porous boron nitride (HPBN) powders is reported. For this purpose, ammonia borane (AB) and polystyrene latex/cetyltrimethyl ammonium bromide (CTAB) were used as BN precursor and inorganic templates, respectively. The as-synthesized material was pyrolyzed at 1150 °C in ammonia atmosphere resulting in the formation of white BN powder. The typical N2 sorption analysis demonstrated formation of porous BN with presence of macro/meso and micropores. Transmission electron microscope (TEM) observations revealed the existence of rather uniform macropores with 55-60 nm in diameter, as well as wormlike mesopores and micropores extended between macropores walls. X-ray diffraction (XRD) and high resolution TEM (HRTEM) analyses displayed the formation of turbostratic-BN with atomic layer distance of 0.37 nm. HPBN powders showed fast adsorption rate of methylene blue (MB) solution and high adsorption capacity of 263.1 mg g-1 for MB at room temperature. © 2014 Elsevier Ltd and Techna Group S.r.l.