The use of a high-energy synchrotron radiation source has permitted the introduction of high-resolution X-ray microtomography imaging as a method of non-intrusive and non-destructive three-dimensional (3D)visualized characterization of porous media. The use of a combination of X-ray microtomography, along with mercury porosimetry and Low Melting Point Alloy (LMPA) intrusion potentially provides a more complete approach to more accurate catalyst pore structure characterisation and modelling. This combined approach has been applied to the study of an industrial alumina catalysts support. The data collected from the study has been used to develop and generate an improved pore network model basis, in which both heterogeneity and hierarchy are considered in obtaining an improved pore architecture and pore size distribution.