Large-molecule polyhydroxy organic acids such as tartaric acid and citric acid were found to significantly promote the cooperative formation of mesoporous silica SBA-15 with homogeneous well-defined hexagonal mesostructure under much weaker acidities without addition of volatile inorganic acids; therefore a novel environmental benign route for SBA-15 synthesis was developed, It is suggested that the polar groups of polyhydroxy acid molecules can greatly strengthen the assembly interactions between the silica species and the triblock copolymer by providing hydrogen bonding. More interestingly, by controlling the strength of hydrogen-bonding interaction that is dependent on the concentration of carboxylic acids, the particle size of the product can be tailored. The silica with small particle size synthesized with a small amount of polyhydroxy acids was favorable support of palladium catalyst for the complete oxidation of volatile organic compounds in atmosphere, probably due to the facilitated diffusion of reactant molecules.