In this paper, we report a facile route, the tin vapor treatment method, to prepare tin oxide containing mesoporous silica composites (TOMS), which display room-temperature photoluminescence (RT-PL). Among them, TOMS-1 and TOMS-2 were synthesized from mesoporous silica SBA-15 and KIT-6, respectively. They are composed of amorphous SiO2 and tin oxide species and they display strong emission near ultraviolet (UV) when excited by UV light. By increasing the preparation temperature, their Sn content can be increased and subsequently their photoluminescence (PL) intensities can be greatly enhanced. Besides, their PL properties are revealed to be closely related to 2-fold-coordinated tin oxygen-deficient centers.