An analysis of pigment traces obtained from an ensemble of marble and limestone finely sculpted architectural elements, kept in the National Archaeological Museum of Cividale del Friuli (Italy), has been performed using scanning electron microscopy (SEM), particle induced X-ray emission (PIXE) and, for the white paint, Raman spectroscopy (RS). The experimental results on six different colours, combined with the historic, stylistic and documentary evidences provided by a recent study, strengthen the hypothesis of the dating and the provenance of all the sculptures in a prestigious building of Cividale in Veneto-Byzantine style, the palace of the Patriarch of Aquileia. The analyses also allow a first insight into the conservation history of the ensemble of architectural decorations.