Microencapsulated finishes are an important element in the development of new textiles. In this context, a large area to be explored is microencapsulation of essential oils in textiles. This technique offers the possibility of developing new products with many advantages over traditional fabrics, as traditional finishing may be ineffective for reasons related to uncontrolled release of the active principle while microencapsulation aims to achieve increased duration of the finishing effect. However, many studies present only the application of microcapsules in a textile but do not report how the release of the encapsulated material occurs or the influence of the textile matrix. This paper reports the mechanism and kinetics of controlled release of microencapsulated citronella oil in cotton and polyester. The microencapsulation was done by complex coacervation with gelatin and gum Arabic as shell materials. The resulting microcapsules were analyzed by optical microscopy, scanning electron microscopy, thermogravimetric analysis, and dynamic light scattering. They were then applied in cotton and polyester and evaluated by attenuated total reflection Fourier-transform infrared spectroscopy. Finally, the controlled release of citronella from the microcapsules deposited on the fabrics was studied in vitro. It was found that the release was directly influenced by the type of fiber: the microcapsules in polyester showed diffusion by a Fickian mechanism, while a non-Fickian kinetic model fit for the modified cotton. Comprehension of such controlled release processes is fundamental for achieving and developing more durable finishing effects