The fabrication of mesoporous silica microcapsules with a highly controlled particle size ranging in the micrometer size presents a major challenge in many academic and industrial research areas, such as for the developement of smart drug delivery systems with a well controlled loading and release of (bio)active molecules. Many studies based on the solvent evaporation or solvent diffusion methods have been developed during the last two decades in order to control the particle size, which is often found to range at a sub-micrometer scale. Droplet-based microfluidics proved during the last decade a powerful tool to produce highly monodisperse and mesoporous silica solid microspheres with a controllable size in the micrometer range. We show in the present study, in contrast with previous microfluidic-assisted approaches, that a better control of the diffusion of the silica precursor sol in a surrounding perfluorinated oil phase during the silica formation process allows for the formation of highly monodisperse mesoporous silica microcapsules with a diameter ranging in the 10 micrometer range. We show also, using optical, scanning and transmission electron microscopies, small angle x-ray diffraction and BET measurements, that the synthesized mesoporous silica microcapsules exhibit a soft-like thin shell with a thickness of about 1 μm, across which 5.9 nm sized mesopores form a well-ordered hexagonal 2D network. We suggest and validate experimentally a model where the formation of such microcapsules is controlled by the solvent evaporation process at the droplet-air interface.