Hydrogen generation from hydrolysis of ammonia borane was investigated using octahedral Au@Pt nanoparticles (NPs) as catalysts. The octahedral Au@Pt NPs were synthesized via a polyol method. Pt NPs were fabricated on the octahedral Au NPs with different atomic ratios of Pt to Au and at different temperatures. The presence of poly(diallyldimethylammonium chloride) as a capping agent is crucial for the successful formation of Pt NPs on the Au nanooctahedra. The synthesized octahedral Au@Pt NPs showed a moderate performance of hydrogen generation from hydrolysis of NH3BH3. The highest catalytic activity of the Au@Pt NPs for the hydrogen generation was observed with activation energy of 44.28 kJ/mol when the Pt coverage on the Au NPs was optimized at the Pt/ Au ratio of 1 and the Pt synthetic temperature of 160 degrees C.