Developing sustainable, efficient and cost-effective materials for adsorptive desulfurization is highly important. Herein, macroscopic 3D boron nitride (BN) monolith has been controllable prepared, with commercial melamine sponge as a template, for the first time and employed for adsorptive desulfurization. By virtue of the 3D framework of melamine sponge, the as-prepared 3D BN monolith inherited the features of high porosity, superelasticity and low density. Compared with the BN powder counterpart, the 3D BN monolith exhibited greatly increased adsorptive desulfurization performance towards various aromatic sulfur compounds. The adsorption capacity over 3D BN monolith achieved amazing 43.2 and 45.2 mg S/g towards dibenzothiophene and 4-methyldibenzothiophene, respectively. This freestanding 3D BN monolith architecture afforded a facile, efficient and recyclable platform for adsorptive desulfurization, which showed great potential for the industrial applications.