Ruthenium (Ru) is one of the most attractive catalysts in the hydrolytic dehygrogenation of ammonia borane. So far, the employed Ru-based catalysts are mainly focusing on hexagonal close packed structured Ru. In this work, we study the crystal phase effect of Ru on the hydrolytic dehygrogenation of ammonia borane, using face-centered cubic structured and hexagonal close packed structured Ru nanoparticles supported on γ-Al2O3. The results show that the catalytic activity is different even these two kinds of Ru nanoparticles hold similar size. Impressively, with the Ru particle size change, the variation trend of activity is opposite for face-centered cubic and hexagonal close packed structured Ru/γ-Al2O3. Finally, some possible reasons for their difference are proposed based on density functional theory calculations.