Confirmed since the twelth century, the Saxon community in Transylvania developed over the years in a rigorous powerful society, with its own lifestyle, social, economic, cultural and artistic standards. Together with research in historic documents, this society is now revealed by material studies of eighteenth– twentieth century objects in the Emil Sigerius collection, preserved in the ASTRA Museum, Sibiu, Romania. Embroideries made in Saxon households as well as representative Saxon coats manufactured in workshops, and dated between 1892 and 1908 (years embroidered on objects), were studied in terms of dye analysis, in order to understand if adoption of new materials goes together with the stylistic improvements. Dye analysis were performed by liquid chromatography with UV–vis and mass spectrometric detection (LC-DAD-MS), nowadays the most appropriate technique for the characterization and identification of colour components in heritage textiles. MS detection, with a triple quadrupole mass analyser, was used to achieve clear identification of each dye in a complex matrix. Construction of suitable spectral libraries through studies on standard dyes and dyed textiles definitely improved the ability to detect natural and early synthetic with greater certainty. Identification of fuchsine (1856), methyl violet (1861), orange II (1876) brilliant green (1879), quinoline yellow (1881) and rhodamine B (1887) in textiles dated about 20 years after the dyes first synthesis prove that transition from natural to synthetic dyes in the Saxon community was very fast, especially for textiles made in specialized workshops. The analytical configurations used prove their competence in textile studies, based on natural and early synthetic dyes research, and promotes the use of advanced analytical techniques in heritage science applications.