We have determined experimentally optical constants for eight thin film materials that can be used in hard X-ray multilayer coatings. Thin film samples of Ni.97V.03, Mo, W, Pt, C, B4C, Si and SiC were deposited by magnetron sputtering onto superpolished optical flats. Optical constants were determined from fits to reflectance-vs-incidence angle measurements made using synchrotron radiation over the energy range E=35-180 keV. We have also measured the X-ray reflectance of a prototype W/SiC multilayer coating over the energy range E=35-100 keV, and we compare the measured reflectance with a calculation using the newly derived optical constants.© (2004) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.