The assessment of the firing temperature of a prehistoric pottery sample collected from ancient Mesopotamia, Turkey was studied using luminescence techniques. The methods for this estimation involved the observation of the thermal and pre-dose sensitization with various re-firing temperatures for both TL and the OSL signals. In the former case, the 110°C TL peak and the rest of the glow curve were used as proxies in this study. In the framework of a first attempt to investigate the impact of grain-size dependence on the sensitization of the luminescence signals, the aforementioned study was performed with four different pottery grain-size fractions: (i) less than 60 μm, (ii) 60–90 μm, (iii) 90–180 μm and (iv) 180–250 μm. The results clearly demonstrated the firing temperature mark of ∼500°C in for the grain size of 90–180 μm, while—as in the case of the lower grain-size fraction—a third proxy, the ratio of the pre-dosed to the thermal sensitization, was seen to indicate the firing temperature. The remaining two grain-size fractions failed to provide any meaningful results with regard to the firing temperature estimation. The dependence of the TL characteristics on the grain size was explained in the framework of the mixed mineralogy.