Developing a low-cost route to synthesize mesoporous TS-1 (MTS-1) is of great importance because of its practical application in industry. Herein, we first synthesized a copolymer containing quaternary ammonium groups by a mesoporous template comprising inexpensive starting materials. Subsequently, waterglass (sodium metasilicate), TiCl3, and copolymer were dispersed in the preformed seeds emulsion, resulting in a gel for synthesizing MTS-1. The counterpart material (CTS-1) was also synthesized by the same procedure except for the absence of the copolymer. Compared with CTS-1, the MTS-1 exhibits good crystallinity and well-defined tetrahedral coordinated Ti species (Ti-IV) in the framework as well as excellent catalytic activity in the oxidation of bulky molecules, such as dibenzothiophene and benzyl phenyl sulfide. This feature may be attributed to the fact that the quaternary ammonium groups on copolymer facilitates the formation of the MFI structure and energetically incorporates the Ti species into the framework.