As structure-directing agents, the molecular structure of surfactants is critical for determining the properties of prepared mesoporous materials. Using dehydroabietic acid as a starting material, a series of rosin-based Gemini surfactants (abbreviated as R-n-R, n = 3, 6, 8 and 10, indicating the carbon atom number contained in the spacer) were synthesized and applied as templates in the preparation of ordered mesoporous silica. The structures and morphologies of the samples were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope and N-2 adsorption-desorption. The R-n-R surfactants feature rigid tricyclic hydrophobic groups with large volumes, which are beneficial for the formation of a three-dimensional cubic phase. Furthermore, the spacer length was found to have a tremendous effect on the structure of the prepared mesoporous silica materials. The head group of R-3-R, which has a short spacer, is excessively charged, leading to silica nanoparticles with an irregular morphology and a rather low BET surface area. With longer spacer lengths, R-6-R, R-8-R and R-10-R are conducive to generating silica nanoparticles with a novel dumbbell-like morphology and with higher BET surface areas of 1171, 1096 and 1186 m(2) g(-1), respectively. The results demonstrate the particularities of the Gemini surfactant structure in the preparation of mesoporous silica nanoparticles with novel morphologies, and the details of the molecular interactions that occur in the condensation of silicate anions are also revealed.