A quantitative analysis is presented for the site-selective Fe K-edge absorption spectra of Prussian Blue: Fe-4[Fe-(CN)(6)](3).xH(2)O (x = 14-16). The site-selective spectra were recorded using high-resolution fluorescence detection lof the Kbeta emission from a polycrystalline sample. The Kbeta fluorescence lines arising from the high-spin and low-spin sites are shifted in energy. Since the emission features partially overlap, fluorescence-detected absorption spectra using different emission energies represent different linear combinations of the pure high-spin and low-spin EXAFS. A numerical method was used to extract the individual site EXAFS spectra from the experimental data. The analysis yields a range of solutions. A unique solution can be obtained if homovalent model compounds are used to simulate the K fluorescence emission from the two Fe sites in Prussian Blue. EXAFS analysis of the range of spectra obtained in the numerical method yields almost identical interatomic distances for the different spectra while the Debye-Waller factors vary considerably. The distances obtained in the EXAFS fit correspond to the crystallographic distances.