With the increasing crisis on energy shortage, hydrogen has been considered as a clean, alternative energy source to replace fossil fuels. As a versatile hydrogen storage material, ammonia borane (AB) has drawn much attention especially for its capacity of producing three-equivalent hydrogen in the presence of suitable catalysts. Here, we demonstrated the use of Au@Cu₂O core@shell nanocrystals with hollow Au particles as core for remarkable catalytic hydrogen production from AB. The hollow Au may provide interior, confined space for stimulating molecular interaction. Moreover, upon protected by the Cu₂O shell, each of the Au core can participate in the catalytic reactions, attaining a homogeneous reaction environment to facilitate the hydrogen production. Under visible light illumination, the catalytic activity of Au@Cu₂O towards AB dehydrogenation can be further enhanced as a result of the photocatalysis capacity of Cu₂O, proven to be a green and economical method of producing hydrogen.