The paint coatings of three energy generators from the 20th‐century powerplant at Levada de Tomar, Portugal, were investigated using micro‐Raman and micro‐X‐ray fluorescence spectroscopies and scanning electron microscopy with energy dispersive spectroscopy. This multi‐analytical approach was used to identify the colouring agents, thus providing a chronological chromatic pallet and allowing to infer on the use of the three energy generators. Together with traditional pigments like Prussian blue, red iron oxide, and carbon black, pigments used in industrial areas like copper phthalocyanine and toluidine red were identified as colouring agents. Complex paint systems of the oldest equipment (1924) were revealed as well as maintenance procedures of the equipment that worked during a longer time (1944–1990). Powdery carbon black layers, resulting from incomplete hydrocarbon combustion and present between metallic substrates and coating layers, suggested the inexistence of paint coatings replacement after the powerplant shutdown. The identification of magnetite as a corrosion product of iron alloy substrate revealed that corrosion developed after the engine shutdown and not during the operation period. The results obtained highlight the potentialities of scientific‐based approach and Raman spectroscopy to the industrial heritage study, an emergent cultural area.