In recent years, search for applicable bidimensional (2D) hydrogen storage materials with high capacity and excellent H₂ physisorption properties has attracted considerable attention from scientists and researchers. According to the rational design, and using first-principles calculations, we propose a t-graphene-like boron nitride monolayer (t-B₄N₄) for hydrogen storage application by replacing C atoms in t-graphene with B and N atoms. The thermal stability and polarization mechanisms of lithium atoms adsorbed at the center of octagons on the t-B₄N₄ system were evaluated at 300 K using ab initio molecular dynamics (AIMD) calculations. Moreover, Li-decorated double-sided t-B₄N₄ can store up to 32H₂ molecules with an average hydrogen adsorption energy of 0.217 eV per H₂ and a maximum hydrogen storage capacity of 12.47 wt%. The reversibility of adsorbed hydrogen was checked and the calculated desorption temperature was 161 K, much higher than the critical point for hydrogen. Based on diffusion barriers, the H₂ molecule diffusion kinetics is faster on the t-B₄N₄ surface than that on t-graphene and graphene.