Short-rotation coppices have potential to be the future source of raw materials for many applications in the wood and paper industries. It is important to establish methods and products to handle their waste biomass. In this paper, the properties of bast fibers extracted from the bark of willow trees (Salix spp.) were evaluated for potential future use in the production of natural fiber-polymer composites. The anatomy of the fibers was investigated through optical and electron microscopy. The thermogravimetric analysis of these fibers showed that the major mass loss occurs at 257 °C. The density of the fibers was measured with a gas pycnometer (1.19 ± 0.2 g/cm3). The chemical analysis showed that willow bark fibers have a composition similar to willow wood. As an indicator of mechanical properties, single willow bast fibers were characterized by tensile tests. The results revealed values for tensile strength (307.6 ± 130.1 MPa) and Young’s modulus (16.9 ± 8.4 GPa) that are comparable to some commonly used natural fibers. The overall results showed that willow bast fibers have the required mechanical properties as well as thermal stability for application in reinforcement of polymers.