Solid state electrochemical energy devices such as batteries, fuel cells and oxygen transport membranes (OTMs) have the potential to revolutionize distributed low-carbon power supply. However, in order to accelerate their commercialization across a range of applications, a much improved understanding of the underlying material microstructure is required. In particular, the rate limiting step of an OTM membrane applied for syngas production is found in concentration losses caused by mass transport limitations. In this field, microstructural parameters, such as tortuosity, porosity and average pore diameter, play a vital role in characterising, comparing and evaluating porous materials. However, unlike the latter two parameters, tortuosity cannot be measured directly which is why different methods have been developed for this purpose. These differ considerably from each other in terms of calculation approach and data preparation techniques. Here, we utilise X-ray nano computed tomography (CT) techniques to reveal the complex microstructure and resolve geometric features affecting mass transport of tubular porous support layers of OTMs to examine the relationship between the pore structure and mass transport (Figure 1). This is achieved via image based tortuosity calculation methods: a fast marching computational technique and a Laplace solver using MATLAB is employed to examine the geometrical tortuosity, and StarCCM+ and COMSOL software packages are used to model the heat flux and effective transport parameters of the porous phase, respectively. In turn, the results are validated using diffusion cell experiments to evaluate the bulk transport properties of the same samples for different binary gas mixtures at different temperatures. Tortuosity is then extracted by applying equimolar and equimass diffusion models [1]. We conclude, that image based calculation methodologies arrive at lower tortuosity values in comparison to diffusion cell experiments (Figure 2). Even the widely used Bruggeman [2] and Maxwell relations prove to be unfit to estimate tortuosity values in the analysed microstructure. The observed difference may stem from Knudsen diffusion effects which are not accounted for in the entirety of tomography based modelling techniques. Secondly, tortuosity values extracted via diffusion cell experiments are a function of gas mixture, temperature and microstructural characteristics rather than a constant value. Consequently, care must be taken in applying purely continuum interpretations of diffusion processes in these complex porous media.