Microcapsules are versatile delivery vehicles and widely used in various areas. Generally, microcapsules with solid shells lack selective permeation and only exhibit a simple release mode. Here, we use ultrathin-shell water-in-oil-in-water double emulsions as templates and design porous ultrathin-shell microcapsules for selective permeation and multiple stimuli-triggered release. After preparation of double emulsions by microfluidic devices, negatively charged shellac nanoparticles dispersed in the inner water core electrostatically complex with positively charged telechelic α,ω-diamino functionalized polydimethylsiloxane polymers dissolved in the middle oil shell at the water/oil interface, thus forming a porous shell of shellac nanoparticles cross-linked by telechelic polymers. Subsequently, the double emulsions become porous microcapsules upon evaporation of the middle oil phase. The porous ultrathin-shell microcapsules exhibit excellent properties, including tunable size, selective permeation and stimuli-triggered release. Small molecules or particles can diffuse across the shell, while large molecules or particles are encapsulated in the core, and release of the encapsulated cargos can be triggered by osmotic shock or a pH change. Due to their unique performance, porous ultrathin-shell microcapsules present promising platforms for various applications, such as drug delivery.