Herein we present methods for synthesizing monodisperse mesoporous silica particles and silica particles with bimodal porosity by templating with surfactant micelle and microemulsion phases. The fabrication of monodisperse mesoporous silica particles is based on the formation of well-defined equally sized emulsion droplets using a microfluidic approach. The droplets contain the silica precursor/surfactant solution and are suspended in hexadecane as the continuous oil phase. The solvent is then expelled from the droplets, leading to concentration and micellization of the surfactant. At the same time, the silica solidifies around the surfactant structures, forming equally sized mesoporous particles. We show that hierarchically bimodal porous structures can be obtained by templating silica microparticles with a specially designed surfactant micelle/microemulsion mixture. Oil, water, and surfactant liquid mixtures exhibit very complex phase behavior. Depending on the conditions, such mixtures give rise to highly organized structures. A proper selection of the type and concentration of surfactants determines the structuring at the nanoscale level. Tuning the phase state by adjusting the surfactant composition and concentration allows for the controlled design of a system where microemulsion droplets coexist with smaller surfactant micellar structures. The microemulsion droplet and micellar dimensions determine the two types of pore sizes.