Nanoframe catalysts containing only small amount of precious metal show very high activities, and therefore have received great attention in recent years. In this work, we report an effective approach for the construction of light-harvesting system to further enhance the catalytic activity of Pd nanoframes by encapsulating Au nanocrystals into the hollow interior of the nanoframes. Catalytic studies show that the as-prepared Au@Pd-frame nanocrystals can significantly enhance the catalytic activity of Pd nanoframes by a factor of 4.5 toward Suzuki coupling reaction under light irradiation.