This study reports a spontaneous selective localization of molecules in crosslinked particles during electrospraying and electrospinning polymer solutions containing the particles. It provides a facile way of preparing microcapsules and fibers with controlled release. The dye molecules were phase separated from the crystalline polymer matrix during the electrohydrodynamic process and moved to the solvent-rich crosslinked particles. The position of the particles in the microcapsules and fibers could be controlled by adjusting compatibility of the particles with the matrix polymer. The microcapsules and fibers did not show the initial burst release of the molecules and gave considerably prolonged release behavior.