Post-Renaissance ceramics (XVI–XIX) obtained in the Emilia Romagna region (north of Italy) demonstrate the difficulty in correctly identifying two different main types of artifacts: (i) enamel terracotta (or majolica) and (ii) glazed engobed terracotta (or mezza-majolica). This problem arises from the fact that the two different artifacts have the same shape, mixture, and even the same decoration in terms of color and style. Based only on macroscopic observation, the distinction between majolica and mezza-majolica could be problematic. This study aims to propose an immediate identification of the finds by diagnostic investigations to achieve identification of the type of coating applied. Different kinds of archeological finds were collected during a restoration of an important building in the city center of Faenza, Italy, and were analyzed by optical transmitted light polarized microscopy on thin sections, scanning electron microscope (SEM-EDS), and colorimetry analysis. The results identified two types of clayey material; one was Fe enriched carbonate clay and the other had Fe enriched non carbonate clay used in the production of the ceramic artifact. The analysis also distinguishes the different techniques by which the artifacts were produced, either by single firing or by double firing.