As an advanced support of TiO2 photocatalyst, mesoporous silica (MS) with hierarchical macroporous architecture (MMS) was prepared by applying templating synthesis techniques. Colloidal crystal of spherical poly (methyl methacrylate) (PMMA) particles and organic surfactant was used for construction of two types of pores with different size scales. The porous structure and state of TiO2 was investigated by various characterization techniques. Mesoporous and macroporous structure of MMS with interconnecting networks was maintained even after loading of TiO2 particles. The unique properties of macroporous structure were observed in the adsorption of acetone gas and 2-propanol gas. In comparison of TiO2-loaded MMS and MS (denoted as TiO2/MMS and TiO2/MS), TiO2/MMS showed a high adsorption rate and a large adsorbed amount in the case of 2-propanol at low and high relative pressure, respectively. However, each profile in the case of acetone was almost same in both samples. Based on the advantageous porous structure, TiO2/MMS also exhibited a good photocatalytic performance in the degradation of 2-propanol in gas phase under UV light irradiation.