A series of porous silica particles is prepared with different concentrations of the fluorinated cationic surfactant 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10)-heptadecafluorodecyl)pyridinium chloride (HFDePC) to trace the changes in pore structure and particle morphology as the surfactant concentration increases. At the lowest concentration studied (1.5 mmol/L), the product consists of small round particles with close-packed cylindrical mesopores. As the HFDePC concentration increases, macroporous voids are introduced to create multi-chambered hollow particles with mesoporous walls. With a still higher concentration of HFDePC the macropore volume decreases, and elongated, tactoid-like nanoparticles are formed with random mesh-phase pores oriented with silica layers perpendicular to the main axis of the particles. Further increasing the concentration of HFDePC eventually leads to the formation of round particles with disordered pores. These changes are consistent with increasing HFDePC concentration favoring increasingly oblate or disklike micelles. The process of forming the elongated particles with random mesh-phase structure is investigated by TEM of chilled and dried samples. The results indicate that the oriented tactoid-like structure forms spontaneously within 2 min by co-assembly of silica and HFDePC rather than by preferred growth perpendicular to the layers. The particle shape and layer orientation are consistent with what would be expected for a liquid-crystal particle with orientation-dependent surface tension. Finally, we compare samples prepared with a high HFDePC and with good or poor mixing. With inadequate mixing, a gel layer forms at the top of the sample which is composed of elongated mesoporous particles with a thick coating of microporous silica. The lower particulate phase contains small disordered particles similar to those obtained in a well-mixed sample. Presumably, the structure of the upper layer results from initial immiscibility of the precursor and slow diffusion of silicates out of the gel.