Organometal-bridged periodic mesoporous catalysts with uniform spheres containing cavities in chambers were synthesized by rapid aerosol-spray assisted co-condensation between organometallic silane and tetraethoxysilane (TEOS) in the presence of cetyltrimethyl ammonium bromide (CTAB) and NaCl double templates. The as-prepared M-PPh2-PMO(H) catalysts (M = Pd2+, Rh+ and Ru2+) were used in various water-medium organic reactions with the aim of diminishing environmental pollution from organic solvents. These catalysts exhibited high catalytic activities and selectivities owing to the high surface area, the uniform distribution of active sites, the ordered mesoporous channels and especially, the cavities as microreactors which facilitated the diffusion and adsorption of organic reactants. Meanwhile, they also displayed strong durability and could be used repeatedly owing to the organometals incorporated into silica walls and the presence of chamber cavities which could effectively protect the ordered mesoporous structure from damage and also inhibit the leaching of active sites.