Microporous silica material AMPS has been synthesized via TEA+ cations assisted self-assembly of silica species in acidic aqueous solution. Nitrogen adsorption analysis revealed 0.65 nm uniform micropores in AMPS, companied with a Langmuir surface area of 745 m2/g and a pore volume of 0.22 cm3/g. The microporous AMPS exhibited an excellent adsorptive performance for volatile organic compounds (VOC) such as cyclohexane and acetone, compared with conventional zeolites such as Y, ZSM-5 and A. The adsorption was rapidly saturated at lower relative pressure with higher capacities than that of conventional zeolites. These features implied promising potentials in the separation and removal of VOCs in the atmosphere by using APS-3.