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Three Transylvanian fragments of some 18th century Saxon tiles obtained from excavations in the Central Railway Station Square in Sibiu (Romania) have been studied by Raman microscopy, FTIR, SEM-EDX and XRF techniques. A lead-rich aluminosilicate was found to have been used as enamel/glaze for the tile fragments. An analysis of the band components of the Raman spectra of the enamel of one fragment in the 400–1200 cm− 1 spectral region indicates that their processing temperature was in the 600–800 °C range, in good agreement with the temperature obtained from FTIR spectra of the other two tile fragments.