Ammonia borane (AB, NH₃BH₃) hydrolysis is an effective strategy for utilizing sustainable hydrogen energy. However, a suitable catalyst is indispensable because this reaction cannot occur kinetically at ambient temperature. In this work, N, O co-doped hierarchical porous carbon materials are facilely prepared from glucose by using K₂CO₃ as the activation agent, followed by employing to confine Ru nanoclusters (NCs) for AB hydrolysis. The proper porous structure of PC-5–700 (S_BET = 1356 m² g⁻¹, V_total = 0.762 cm³ g⁻¹, V_micro/V_total = 56.0%), which is prepared with a mass ratio of 5: 1 for K₂CO₃ to glucose and calcined at 700 ℃, are beneficial to the high dispersion of Ru NCs. Additionally, the doped heteroatoms increase the hydrophilicity of the materials, enhancing the active site accessibility in polar solvents. Also, the lone pair electrons of N and O can form chelation with Ru³⁺ ions, facilitating Ru dispersion and enhancing the surface electronic density. As a result, PC-5–700 confined Ru NCs with a mean size of 1.3 nm display excellent catalytic performance in the hydrolytic dehydrogenation of AB. The corresponding turnover frequency (TOF = 1143.77 min⁻¹) and specific hydrogen evolution rate (r_B = 298400 mL min⁻¹ g_Ru^-1) at 30 ℃ in the alkaline solution are superior to many previous results, verifying a promising potential in the hydrolysis of solid-state chemical hydrogen storage.