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The CNT bundles can be jagged and used as template to load the precursor H₂WO₄. The H₂WO₄ seeds can be enclosed by the jagged CNT template during liquid precipitation process. The H₂WO₄clusters with avarage size of 500Snm are consisted of nanosized H₂WO₄with 10-20 nm diameter, which display high specific surface area of 85.24 m₂ g_-1 and total pore volume of 0.2933 m₃ g_-1. After thermal treatment of H₂WO₄/CNTs at oxygen atmosphere, nano-WO₃ particles attached to sphere-like micro-WO₃ can be easily obtained by removing the CNT template. Its specific surface area and total pore volume is 18.7 m₂ g_-1 and 0.2055 m₃ g_-1respectively. These results indicate that the jagged CNTs can play an important role for effective mediation of WO₃ with hierarchical size, and exhibit excellent prospects for preparation of micro-nanostructured materials.