The concave behaviour of the Porod invariant observed during the calcination of CaCO3 powder samples suggests the following picture of the evolving internal structure of the samples. The outset sample is formed by a crystalline CaCO3 phase and a void phase. During the calcination, the first phase shrinks in volume at fixed density since the temperature increase breaks down the crystalline structure at the interface, leading to the formation of an amorphous phase comprising an equal number of CO2 and CaO atomic groups. The last groups gradually condense, forming a third phase of solid CaO of constant density and increasing volume fraction, while the companion CO2 groups flow out of the sample. The amorphous phase occupies, with a variable density, all the volume left free by the other two phases. At the end of the calcination, both the volume fraction of the first phase and the density of the amorphous phase vanish so that the sample will again be made up of two phases: the voids and the solid CaO. Best‐fitting the resulting theoretical expressions of the Porod invariant and of the Porod law coefficient to the observed values, one can determine the matter densities, volume fractions and specific surface areas of the phases. The chemical structures of the phases of CaCO3 samples undergoing a calcination process, as well as the volume fractions and matter densities of those phases, are determined by the Porod invariant behaviour.