Macroporous silica (MS) and macro/mesoporous silica (MMS) were prepared by spray drying a polystyrene (PS) latex sol containing a silica source, followed by calcination. As a silica source, 3-aminopropyl triethoxysilane (APS) was used for MS while either silica sol (SS) or tetraethoxyothosilicate using P123 templating (P123-TEOS) was used for MMS. Spray drying and calcination could also take place in a once-through aerosol reactor. The transformation of the silicon alkoxides to silica and decomposition of PS occurred at similar temperatures. Therefore, for APS-originated MS, the metal additives such as silver and nickel were required to accelerate the former. In addition, the nickel was well dispersed in the silica matrix during calcination even at 800 ℃, in turn to thermally stabilize the porous structures. The wall-preforming additives were unnecessary for PS/SS and PS/P123-TEOS, since the SS drying and P123 templating, respectively, took place at lower temperature than PS decomposition. The porosities of all the porous silica prepared ranged from 0.54 to 0.57, which were close to the volume fraction of PS in the PS-alkoxides mixture solidified right after spray drying.