A series of hierarchically structured porous silica sphere (HSPSS) materials are successfully fabricated by a facile, one-step microemulsion/vesicle bimodal method in a multicomponent microemulsion system of P123/n-butanol/1,3,5-trimethylbenzene/KCl/H2O (surfactant/cosurfactant/oil/salt/water). The pore structures of the obtained HSPSS products consist of mesocellular foam and mesostructured vesicles. In contrast to the traditional porous silica materials the new structures combine two separate, distinct mesophases with different-sized mesovoids in a single porous sphere. Moreover, the proportion of every mesophase in obtained HSPSS can be easily adjusted by tuning the initially added amount of n-butanol or KCl in this multicomponent microemulsion system. When the molar ratio of KCl/tetraethoxysilane is 2.15, the obtained HSPSS material is turned into uniform mesostructured vesicle silica spheres, which consist of many small diameter vesicle particles. The hydrodesulfurization (HDS) activity of fluid catalytic cracking diesel over the HSPSS was tested. HSPSS-0.75-1.43 catalyst support with multiple mesoporous structures shows the highest HDS efficiency (98.5%) among all the studied catalysts.