There is renewed interest in using advanced techniques to characterize ancient Roman concrete. In the present work, samples were drilled from the "Hospitium" in Pompeii and were analyzed by synchrotron microtomography (μCT) and neutron radiography to study how the microstructure, including the presence of induced cracks, affects their water adsorption. The water distribution and absorptivity were quantified by neutron radiography. The 3D crack propagation, pore size distribution and orientation, tortuosity, and connectivity were analyzed from μCT results using advanced imaging methods. The concrete characterization also included classical methods (e.g., differential thermal-thermogravimetric, X-ray diffractometry, and scanning electron microscopy). Ductile fracture patterns were observed once cracks were introduced. When compared to Portland cement mortar/concrete, Pompeii samples had relatively high porosity, low connectivity, and similar coefficient of capillary penetration. In addition, the permeability was predicted from models based on percolation theory and the pore structure data to evaluate the fluid transport properties.