For the first time, μ-X-ray fluorescence (μ-XRF) mapping combined with fluorine K-edge μ-X-ray absorption near-edge structure (μ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substance (PFAS) contamination and inorganic fluoride in sample concentrations down to 100 μg kg⁻¹ fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheets) were investigated. μ-XRF mapping allows for a unique element-specific visualization at the sample surface and enables localization of fluorine containing compounds to a depth of 1 μm. Manually selected fluorine rich spots were subsequently analyzed via fluorine K-edge μ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded μ-XANES spectra. Complementarily, solvent extracts of all samples were target-analyzed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 μg kg⁻¹ dry weight (dw). All environmentally exposed samples revealed a higher concentration of PFAS with a chain length > C₈ (e.g. 580 μg kg⁻¹ dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C₄ to C₈. Independent of quantified PFAS amounts via target analysis, μ-XRF mapping combined with μ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples.