Hierarchically porous silica-aluminum is an important support material for metal-catalysts, because of its excellent properties. Herein, an efficient hydrothermal approach for the production of hierarchical aluminum- doped silica (Al-SiO₂) architectures was reported by employing aluminum nitrate as an aluminium source and TEOS as silicon source. Effects of the structure-oriented agent on the structure of Al-SiO₂ were investigated. Structural features of Al-SiO₂ were characterized by XRD, SEM and N₂-physisorption. The results showed that hierarchical Al-SiO₂ with "worm-like" porous of 30-40 nm can be synthesized by using TPAOH as the structure-oriented agent and hydrothermal treatment at 80 ℃. The cobalt catalysts were prepared by the wetness impregnation method. Compared with commercial SiO₂ supported cobalt catalysts, the Fischer-Tropsch synthesis performance of the catalyst Co/Al-SiO₂ is significantly enhanced, i.e., CO conversion nearly doubled, CH₄ selectivity reduced by 19.3wt%, C₂-C₄ selectivity reduced by 13.3wt%, and the selectivity of gasoline products (C₅-C₁₂) reached 53.3wt%.