The Royal Society of Chemistry. Borane-amine adducts (H3N·BH3, AB) in tetrahydrofuran solution were infiltrated into polypyrrole (PPy) nanotubes by a capillary effect, forming an ammonia borane (AB)@PPy combined system. This composite system combines the synergetic catalysis of nitrogen atoms with nanoconfinement in nanotubes, resulting in a significant improvement in the dehydrogenation properties. Dehydrogenation results showed that the AB loaded on PPy can release 15.3% hydrogen below 150 °C with an onset decomposition temperature as low as 48 °C. More importantly, the evolution of harmful ammonia, diborane, and borazine was entirely suppressed.