Decomposition and precipitation processes in a binary Al–Li alloy and a technical Al–Li–Cu–Mg alloy were investigated using differential scanning calorimetry and X-ray Raman spectroscopy (XRS). The formation of 𝛿' and T1 precipitates in the Al–Li and the T8 heat-treated Al–Li–Cu–Mg alloy, respectively, was confirmed using DSC. The XRS measurements complemented by simulated spectra allowed for probing specifically Li and its environment within the Al matrix. Based on linear combination fits of

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... e XRS spectra, the relative contributions of 𝛿′ and T1 precipitates were quantified. These results are in agreement with estimates of the relative amount of Li taking part in the precipitation process. Difficulties and limitations of the application of XRS to Al alloy systems are also discussed.