Nano-silver composites with a thermoplastic polyurethane as the matrix were prepared by two different routes. Using the so-called in situ preparation, silver nanoparticles were obtained by a thermal reduction of silver acetate during melt mixing. In addition, a more sophisticated ex situ preparation method was developed. Here, the silver nanoparticles are synthesized in an invertible polyester resulting in much smaller particle sizes. The particles obtained are surrounded by the polyester cage, which stabilizes them with respect to agglomeration. Hence, an incorporation of those particles into a polymer melt with common techniques like extrusion leads to an even distribution. This is due to the fact that the invertible polyester and the polymer matrix are entirely miscible which was proven with DSC measurements. The silver ion release of the composites prepared was measured with anodic stripping voltammetry. At a constant weight percentage of silver in the polymer, the composite with the ex situ silver nanoparticles exhibits a silver ion release which is about two orders of magnitude higher than the release from the composite with the in situ silver nanoparticles. This observation is explained by the higher specific surface area of the smaller particles and a higher coefficient of diffusion for silver ions. A concentration of only 0.07 wt% silver nanoparticles, prepared with the ex situ method, exhibits a high enough release of silver ions to achieve antimicrobial properties.