The present article focuses on an interdisciplinary research on cultural heritage concerning the microanalysis of Gothic mural paintings made during the 15th century in Slovenia. The samples were chosen from the churches of Crngrob (1453), Mirna (1463–1465), Mevkuž (1465) and Mače (1467), attributed to two of the most important Gothic painters of that period of time: Master Bolfgang and Master of Mače. The chemical and phase composition of all the mortars, number of their layers and selection of the pigments were of interest. For this purpose, fragments of mural paintings were studied with several instrumental techniques: optical microscopy (OM), SEM‐EDX, x‐ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). In early artworks, the mortar was made using a mixture of lime and more or less clean sand. Later, crushed lime‐rock or marble instead of sand was added to lime. The pigments identified by EDX microanalysis of cross sections previously studied by OM, are of earth or mineral origin. Therefore, they are durable in fresco and lime techniques: lime white, yellow and red natural or burned ochres, green earth and azurite. The results confirmed the high technical quality of both painters and the relationships between the teacher and the disciple. Master Bolfgang and Master of Mače combine three basic techniques of mural painting: fresco, secco and lime techniques. This kind of investigation and methodology allow us to know better the Central European Art and the Slovenian Art in the Adriatic zone, as well as the general map of European Art in the 14–15th centuries. Copyright © 2008 John Wiley & Sons, Ltd.