In this work, a facile method was developed for fabrication of mesoporous bioactive glasses (BGs) with controlled shapes using cetyltrimethylammonium bromide (CTAB) as templating agent for sol–gel process. The morphologies, specific surface areas and pore sizes of the BGs were characterized by FE-SEM, TEM, and the BET and BJH methods, respectively. Rod-like BGs with mesoporous structures and high specific surface areas were prepared using CTAB as the templating agent. The shaping of the samples depicted a dynamic process from sphere to short rod then to long rod as the CTAB concentration was increased. This study presents an effective approach for controlling the spherical and rod-like structures of BGs.