Clay-based materials are the most traditional components of buildings. To improve their performance in a sustainable way, agents can be mixed to fired clay acting as a pore-forming factor. However, firing temperatures highly influence their microstructure which is closely linked to a material’s final performance as a ceramic block. To highlight the influence of the firing temperature on microstructure, and more specifically on the pore size distribution of clay-based materials, three innovative porous materials were manufactured. These materials were produced by mixing clay and pore-forming agents. They were characterized by optical and scanning electronic microscopy, x-ray diffraction, mercury intrusion and nitrogen adsorption. These techniques allow the phase identification of materials, show sample microstructure and quantify the pore size distribution at different scales. Furthermore, geometric parameters of sample microstructure such as grain diameter and roundness are estimated by using computer software. To conclude, results provide an enlightenment about the influence of material microstructure on the pore size distribution at two firing temperatures. These results can be useful to allow the tune of porous characteristics and, therefore, contribute to the production of more sustainable construction materials.