AbstractThe synthesis of hierarchically porous materials usually requires complex experimental procedures, often based around extensive trial and error approaches. One common synthesis strategy is the sol–gel method, although the relation between synthesis parameters, material structure and function has not been widely explored. Here, in situ 2D hard X‐ray ptychography (XRP) and 3D ptychographic X‐ray computed tomography (PXCT) are applied to monitor the development of hierarchical porosity in Ni/Al₂O₃ and Al₂O₃ catalysts with connected meso‐ and macropore networks. In situ XRP allows to follow textural changes of a dried gel Ni/Al₂O₃ sample as a function of temperature during calcination, activation and CO₂ methanation reaction. Complementary PXCT studies on dried gel particles of Ni/Al₂O₃ and Al₂O₃ provide quantitative information on pore structure, size distribution, and shape with 3D spatial resolution approaching 50 nm, while identical particles are imaged ex situ before and after calcination. The X‐ray imaging results are correlated with N₂‐sorption, Hg porosimetry and He pycnometry pore characterization. Hard X‐ray nanotomography is highlighted to derive fine structural details including tortuosity, branching nodes, and closed pores, which are relevant in understanding transport phenomena during chemical reactions. XRP and PXCT are enabling technologies to understand complex synthesis pathways of porous materials.