X-ray W/B multilayer mirrors with a period of 2.5 nm were deposited by dc magnetron sputtering and studied in comparison with W/Si multilayer systems of the same period. Transmission electron microscopy, grazing incidence X-Ray reflectivity, and x-ray photoelectron spectroscopy analysis revealed that the layer quality and interfaces of the W/B multilayers are not better than those of the W/Si multilayers. Strong intermixing between W and B is present, which leads to compound formation with little or no pure W left after the interaction: an optically unfavorable boride formation and an increased roughness result in a reduced reflectivity. The deposited W/B multilayer mirrors showed a reflectivity of 34.5% at 0.84 nm and angle of incidence 9.7°, compared to 40% obtained for W/Si multilayers. Ion polishing applied on the boron layers did not result in improvements of the reflectivity.