To explore the ideal architecture of Pt-Co bimetallic catalyst for aromatics saturation, various Pt-Co bimetallic catalysts were synthesized via the galvanic replacement, the co-impregnation, and the sequential impregnation methods, and were characterized by CO chemisorption, transmission electron microscopy (TEM), H2-temperature-programmed reduction (H2-TPR), H2-temperature-programmed desorption (H2-TPD), X-ray fluorescence (XRF) spectrometry, and inductively coupled plasma atomic emission spectroscopy (ICP-AES), while the catalysts were evaluated by the flow reactor study of toluene hydrogenation. These characterization results suggest that the surface decoration of Pt has little influence on the number of active sites located on the surfaces of the reduced Co-based catalysts, but can greatly suppress the oxidation of Co at room temperature and provide the activated hydrogen at a relatively low temperature. It is demonstrated that their chemical properties and catalytic performance are largely dependent on the location of Pt atoms in the bimetallic catalysts. The architecture of Pt-Co bimetallic catalyst consisting of Co/SiO2decorated with 0.3% of Pt, with the most of Pt atoms being situated on the surfaces of Co nanoparticles, is the active structure for aromatic saturation and has the maximum utilization of Pt.