A micro-mesoporous inorganic-organic hybrid material PAF-12, derived from octaphenylsilsesquioxane (OPS, [C6H5(SiO1.5)]8) as basic building units, was successfully synthesized via Suzuki cross-coupling reaction. Thermogravimetric analysis (TGA) shows that PAF-12 is thermally stable up to 500 àin air condition. According to Ar sorption isotherm, the network of PAF-12 shows classic type IV isotherm and also exhibits a sharp uptake at low relative pressures indicating micro-mesoporous texture. The pore size distribution of PAF-12 calculated from non-linear density functional theory (NLDFT) gives only two clear narrow peaks centered at 1.57 and 3.17 nm. To the best of our knowledge, PAF-12 is the first hybrid material containing both micropore and mesopore reported for silsesquioxane-based materials. Additionally, PAF-12 exhibits high adsorption abilities for organic chemical pollutants such as benzene and methanol. The effects of different solvent systems to synthesize PAF-12 were also investigated and the optimal condition was found out.