Magnesium potassium phosphate ceramics are chemically bonded ceramics employed as biomaterials, in nuclear waste encapsulation and for concrete repair. The microstructure dictates material performance and depends on the raw mix composition. Synchrotron X-ray computed microtomography was employed to describe the 3D microstructure and its time evolution during hardening and gain insights into the reaction mechanisms. Any excess water with respect to the stoichiometry of the reaction brought about an increase in porosity, but, notably, a reduction in the average pore size. Crystals filled the water pockets' in the ceramic volume by growing larger, although less densely packed, increasing the complexity of the pore shape. Platelet over elongated crystal habit was favoured. Such a change in shape is likely related to a change in reaction mechanism, as crystallization from a gel-like amorphous precursor is hindered and progressively substituted by a through-solution mechanism. It is proposed that the time evolution of the microstructure is dictated by the balance between crystallization from amorphous precursor, prevailing in relatively dense' systems (with stoichiometric water or in low excess), and water segregation, prevailing at higher water contents. The former mechanism was shown to produce an increase in porosity with time, because of the density mismatch between the amorphous and the crystalline phase.