In this X-ray absorption near-edge structure (XANES) study we focused our interest on co-precipitated Fe and Cr fluorides. Compounds with a low Cr content are catalytically active in the dehydrochlorination of 1,1,1-trichloroethane. XANES reveals for these samples an incorporation of a modified CrF3-x(OH)(x) pyrochlore structure into the beta-FeF3 host lattice and an electron-deficient Cr 3d orbital, which may act as a Lewis acid site in the catalytic process.