In St. Jacob’s parish church in Ormož, Slovenia, mural paintings from around 1350–1370 are partially conserved in the northeastern corner of the main nave. They are almost completely black, indicating a large-scale pigment degradation. They were studied as a part of a larger research project aiming to identify materials applied and their possible degradation. First, they were studied in situ, and next, extracted samples of plaster, pigments, and colour layers were analysed by optical microscopy, Raman spectroscopy, FTIR spectroscopy, SEM-EDS, and XRD. Haematite, green earth, malachite, azurite, and tenorite were identified, showing that azurite and perhaps also malachite degraded to black tenorite, probably due to their fine grinding and their application directly on the fresh plaster. The plaster is made with small and large amounts of aggregate with mostly quartz with some impurities, which makes it fragile. The original appearance of these murals was of bright blue and green colours.