The effects of mesoporous structure on grain growth were investigated in this study. The synthesis was accomplished using block copolymer as the organic template and tungsten chloride as the inorganic precursor. Thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy, x-ray diffractometry (XRD), transmission electron microscopy, and N2 adsorption/desorption isotherms were used to characterize the microstructures obtained for different temperatures. TGA and XRD analyses demonstrate that copolymers were expelled at 150–250 °C, and mesoporous structure was stable up to 350 °C. The pore diameter and the surface area evaluated from the Barrett-Joyner-Halenda model and Brunauer–Emmett–Teller method indicated that the average pore diameter is 4.11 nm and specific surface area is 191.5 m2/g for 250 °C calcination. Arrhenius equation used to calculate the activation energy for grain growth demonstrates that the activation energy for grain growth was about 38.1 kJ/mol before mesostructure collapse and 11.3 kJ/mol after collapse. These results show evidence of two different mechanisms governing the process of grain growth. The presence of the pore can be related to the obstacle for grain growth.