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The changes in brick porosity upon firing (700 up to 1100 °C) and its relation to the mineralogical composition are examined. Two types of raw clay with a composition representative of that used in brick-making industry were selected to manufacture the bricks: one contains notable amounts of carbonates, with a grain size of under 1 mm, and the other is predominantly quartzitic and lacking in carbonates. We demonstrate that the presence or absence of carbonates strongly influences the porosity development and, therefore, the brick texture and physical-mechanical properties. The carbonates in the raw clay promote the formation of fissures and of pores under 1 μm in size when the bricks are fired between 800 and 1000 °C. The absence of carbonates results in a continuous reduction in porosity and a significant increase in the pore fraction with a radius (r)>1 μm as the firing temperature rises and smaller pores coalesce. Porosity and pore size distribution results obtained from the combined use of hydric tests (HT), mercury intrusion porosimetry (MIP) and digital image analysis (DIA) of scanning electron microscopy photomicrographs are compared. A clear correlation between the water absorption and drying behaviour of the bricks and the porosity plus pore size distribution is observed. DIA discloses the evolution of size, shape and connectivity of macropores (r> 1 μm) and evidences that MIP results underestimate the macropore content. Conversely, MIP gives a good estimate of the open porosity and of the distribution of pores with r<1 μm. It is concluded that the combined use of these complementary techniques helps to fully characterise the pore system of bricks. These results as well as the study of the evolution of the speed of ultrasound waves vs. time yield useful information to evaluate the bricks physical–mechanical behaviour and durability. The relevance of these findings in the conservation of historic buildings is discussed. [Copyright &y& Elsevier]