Hierarchical macro-mesoporous Pt/NiO hollow microspheres are synthesized and used for catalytic decomposition of formaldehyde in air at room temperature. The uncalcined Pt-Ni(OH) 2 sample exhibits low catalytic activity.T he Pt/NiO sample heateda t3 00 8Cs hows significantly enhanced catalytic activity.T he Pt/NiO sample at 400 8Ce xhibits the highest catalytic activity,m ainly due to its bimodal macro-mesoporous structure with open and accessible pores, which provides al arge specific surface for HCHO ad-sorptiona nd Pt dispersion, enables the fast diffusion and transport of gas molecules,a nd ensures the accessibility of active sites on Pt nanoparticles for gas molecules. Moreover, all Pt/NiO hollow spheres have higher catalytic activity than Pt-decorated commercial NiO. The preparedh ierarchical macro-mesoporous Pt/NiO nanocomposite hollow microspheres should also find applications in adsorption, photocatalysis, electrocatalysis, separation, and purification processes.[a] Dr.