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At the beginning of the 20th century, the eclectic artist Mariano Fortuny y Madrazo patented two innovative methods for polychrome printing on fabrics and textiles, giving life to Fortuny fabric production in Venice. The first patent was related to colour application, while the second to a special machine that allows continuous printing using cylindrical rollers. Despite the descriptions, the methodology and materials used remain a secret. In collaboration with the Fortuny Museum in Venice, this research aimed at studying and identifying the different steps of Fortuny printing methodologies. Printing matrices, fabrics and raw materials found in the artist's studio were analysed in a multi-analytical campaign through digital microscopy, X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy in attenuated total reflectance (FTIR-ATR), μ-Raman spectroscopy and gas chromatography–mass spectrometry (GC–MS). Three main pigments were identified in paper samples: ivory black, a copper-based pigment, and a carbon black pigment with ultramarine for blues. The pigments were bound with linseed oil and colophony in varying proportions. Polychrome silk fabrics were dyed with a base colour, and then the coloured patterns were superimposed by continuous printing. Prussian blue was identified as one of the textile inks. Results provided a better understanding of printing methodology. [ABSTRACT FROM AUTHOR]