Porous and amphiphilic polymer microspheres were incorporated into polyurea capsules in order to control the release of the core solvents independently of wall formation. While nonpolar poly(divinylbenzene-55) microspheres were simply encapsulated along with the xylene core solvent, the amphiphilic poly(divinylbenzene-55-alt-maleic anhydride) microspheres, as well as maleic acid functionalized poly(divinylbenzene-55) microspheres, became embedded at the polyurea−water interface. Release of xylene from these microcapsules into air was monitored at room temperature and 50 °C. Release profiles change significantly upon addition of amphiphilic porous microspheres, with the release rates scaling with microsphere loading. Scanning transmission X-ray spectromicroscopy (STXM) indicates that the polyurea is largely excluded from the pores of the microspheres.