Ordered mesoporous silica thin films using block copolymer have drawn an attention for low-k application due to its ordered pore structure. From the respect of dielectric and mechanical properties of the film, there is trade-off between pore size and wall thickness. In this work, factors for increase of wall thickness were investigated. It was found that body-centered cubic structure was maintained irrespective of the concentration of catalytic acid. The catalytic acid thickens the framework wall because counterion reduces the repulsion force between silicic acids. The highly ordered mesoporous silica films were obtained although high concentration of acid was added to the silica sol. However, wormlike micelle exists more with high HCl concentration due to fast gellation rate. And excess water, which has the role similar to the humid atmosphere, also increases the thickness of silica wall. However, large amount of excess water at the micelle interface disrupts organic-inorganic electrostatic interaction. As a conclusion, optimization of HCl concentration in the silica sol and control of humidity during spin coating can simultaneously increase the framework thickness while maintaining the pore periodicity. (C) 2006 Elsevier B.V. All rights reserved.