The invention discloses a preparation method of three-dimensional porous hexagonal boron nitride. The preparation method comprises steps as follows: step one, a precursor is placed into a crucible, wherein the precursor comprises a nitrogen source and a boron source, the nitrogen source is one or more of ammonia, urea, sodium azide, pyridine, melamine and ammonia borane, and the boron source is one of boron powder, boron oxide, boric acid, ammonium borate, sodium borohydride, boron carbide and ammonia borane; step two, the crucible is placed in a high-temperature furnace, vacuum pumping is performed to 1-40 Pa, gas is introduced and oxygen is eliminated; step three, the temperature is increased to 900-1,600 DEG C in 10 min-4 h, and a reaction is performed for 0.5-5 h; and the temperature is reduced to the room temperature, and three-dimensional porous hexagonal boron nitride is obtained. The preparation method of three-dimensional porous hexagonal boron nitride is simple in technology, complex raw material pretreatment and follow-up treatment are not needed, the repeatability is good, batch preparation can be achieved, and industrialized application is easy to achieve.