This paper presents mass transfer models of the release process from hierarchical dispersed systems such as multiple emulsions and micro/nanospheres. The models were validated by experimental data of an active component released from multiple emulsions and microspheres obtained via multiple emulsion thermal cross-linking. The simulations of release profiles confirmed the importance of the internal structure of multiple emulsions/microspheres, as well as the intensity of external mixing in the modeling of the controlled release process. The models presented allowed the mass released to be determined within satisfactory agreement with experimental data after optimization of parameters that describe internal emulsion/microsphere structure. The model proposed for describing the release process from microspheres can simulate release profiles that exhibit phasic behavior (primary/lag and continuous release). The model simulations were extended to nanoscale particles with satisfactory results.