Microcapsules for controlled chemical release and uptake are important in many industrial applications but are often difficult to produce with the desired combination of high mechanical strength and high shell permeability. Using water-oil-water double emulsions made in microfluidic devices as templates, we developed a processing route to obtain mechanically robust microcapsules exhibiting a porous shell structure with controlled permeability. The porous shell consists of a network of interconnected polymer particles that are formed upon phase separation within the oil phase of the double emulsion. Porosity is generated by an inert diluent incorporated in the oil phase. The use of undecanol and butanol as inert diluents allows for the preparation of microcapsules covering a wide range of shell-porosity and force-at-break values. We found that the amount and chemical nature of the diluent influence the shell porous structure by changing the mechanism of phase separation that occurs during polymerization. In a proof-of-concept experiment, we demonstrate that the mechanically robust microcapsules prepared through this simple approach can be utilized for the on-demand release of small molecules using a pH change as exemplary chemical trigger.