Highly ordered small pore mesoporous silicas were synthesized by using a mixture of surfactants as a template. The surfactant system comprises short-chain cationic surfactant (decyltrimethylammonium bromide, denoted C(10)TMAB) and sodium salicylate (sodium o-hydroxybenzoate, denoted SS). Addition of SS into a C(10)TMAB system can effectively reduce the surfactant head-group repulsion by screening the electrostatic charge, optimizing the surfactant packing, thus facilitating the synthesis of highly ordered small pore mesoporous silicas.