AbstractThe volume ratio of toluene to N,N‐dimethylformamide (DMF) was adjusted during the amine functionalization of SBA‐15 to change the amine content of SBA‐15. XPS, FTIR, and TGA analyses indicated that under the experimental synthetic conditions the number of amine groups varies with the ratio of toluene/DMF, and the highest content of amine could be obtained with a volume ratio of toluene/DMF = 3:2. The hydrogen production experiment of formic acid decomposition showed that the hydrogen production efficiency over the Au‐Pd‐SBA‐15‐NH2 catalysts increased with the increase in the surface amine content of the Au‐Pd‐SBA‐15‐NH2. The optimal Au‐Pd‐SBA‐15‐NH2‐TD (toluene/DMF = 3:2) catalyst proved to have the smallest Au‐Pd bimetal nanoparticle size and exhibited a turnover frequency (TOF) = 631 hours−1 and an activation energy (Ea) = 20.8 kJ · mol−1 at 25°C. The catalytic performance of hydrogen generation from the formic acid was improved due to the synergistic effect between the amine‐functionalized SBA‐15 and the Au‐Pd bimetal (metal‐support interactions).