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• Machine Learning to classify watermarked Italian paper. • XRF and FTIR spectroscopies to study late middle-aged Italian watermarked paper. • A new spatial-temporal approach to trace the local recipes and the geographical paper mills' production. • Bergamo and Bologna stand out as marked watermarked Italian paper mills. Manuscripts, illuminated codex, books, documents and letters are composite materials, traces of the past starting from the invention of the writing. In this context, dating is one of the most important information for document attribution, and watermarked papeItaly'smarkers for studying their time-spatial distribution. In the Late Middle Ages, Italy's most important centre of paper mill was located in the town of Fabriano (Marche region, Italy). Here, a selection of ten Italian Late Middle Ages watermarked papers belonging to the Corpus Chartarum Italicarum (Corpus of Italian papers) is characterised by elemental and molecular spectroscopies and collected data are analysed by Machine Learning (ML) to trace the local fabrication recipes and the geographical paper mills production. Data from portable X-ray fluorescence and Fourier transform infrared spectroscopy were analysed through Singular Vector Machine, Soft Independent Modeling of Class Analogy and Moving Blocks methods. This innovative ML spatial-temporal approach based on keeping the temporal variable fixed is used to find elemental benchmarks for classifying the watermarked Italian notarial catalogue of the Late Middle Ages finding differences in the local recipes and studying the homogeneity in the paper mills' production. Results show that watermarked paper from Northern Italy, from the town of Strozza, Piacenza and Bergamo , as well as Bologna, present a high elemental and molecular homogeneity, which indicates that the hand-made processing technique could be the same helped by the proximity of the three cities, starting point for technologies exchange or influence. No heavy metals are found in the watermarked paper and K, Ca, Fe and Zn are identified as elemental benchmarks. Finally, Ca, Ti, Mn, Cr and Fe are particularly present on the edges of the watermarked papers. [Display omitted] [ABSTRACT FROM AUTHOR]