This work involved the first-ever characterization of antique Portuguese ceramic wall tiles in the Historic Center of São Luis do Maranhão, Brazil. The tiles were characterized by optical microscopy, X-ray diffraction (XRD) and chemical analysis to identify the possible raw materials used in the fabrication process, as well as the firing temperature of these materials. The results indicate that the microstructure of these materials consists of pores of varying sizes with calcite incrustations and quartz grain sizes smaller than 500 µm distributed in a pinkish yellow matrix, which were identified by XRD as calcite, gehlenite, wollastonite, quartz, and amorphous mineral phases. Based on this information, it can be inferred that the original raw materials probably consisted of a mixture of kaolinitic clays (Al2O3·2SiO2·2H2O) rich in calcium carbonates and quartz, or mixtures of kaolinitic clays, quartz and calcite, which did not reach the pre-firing temperature of 950ºC.