It has been established that the durability of cement-based composites is generally controlled by the transport characteristics of fluid in their pore network. Experience has shown that the monitoring of transport properties, such as the coefficient of permeability, in the laboratory is a very exhaustive task. The pore network in a cementitious composite, which provides passage for fluid transportation, is a major controlling factor for transport characteristics. In the last few years, many efforts have been made to correlate the microstructure and the coefficient of fluid permeability, and/or diffusion, for a cementitious composite. In this study, a set of ordinary Portland cement (OPC) and OPC/fly ash mortar samples equilibrated in different relative humidity were analysed using PORECOR analysis and the coefficient of oxygen permeability was calculated and compared with the coefficient of permeability of another set of the same samples tested in the laboratory, and valid statistical correlation was obtained.