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The development of capsules with additives that can be added to polymers during extrusion processing can lead to advances in the manufacturing of textile fabrics with improved and durable properties. In this work, caffeine (CAF), which has anti-cellulite properties, has been encapsulated by liquid-assisted milling in zirconium-based metal–organic frameworks (MOFs) with different textural properties and chemical functionalization: commercial UiO-66, UiO-66 synthesized without solvents, and UiO-66-NH2 synthesized in ethanol. The CAF@MOF capsules obtained through the grinding procedure have been added during the extrusion process to recycled polyamide 6 (PA6) and to a biopolymer based on polylactic acid (PLA) to obtain a load of approximately 2.5 wt% of caffeine. The materials have been characterized by various techniques (XRD, NMR, TGA, FTIR, nitrogen sorption, UV–vis, SEM, and TEM) that confirm the caffeine encapsulation, the preservation of caffeine during the extrusion process, and the good contact between the polymer and the MOF. Studies of the capsules and PA6 polymer+capsules composites have shown that release is slower when caffeine is encapsulated than when it is free, and the textural properties of UiO-66 influence the release more prominently than the NH2 group. However, an interaction is established between the biopolymer PLA and caffeine that delays the release of the additive. [ABSTRACT FROM AUTHOR]