The mechanism of fluid and heat transmission within materials with complex porous structures has not yet been fully explored and understood using basic analytical techniques. Therefore, the lack of advanced equipment and techniques has left an important knowledge gap in explaining the complex mechanisms of fluid motion and heat transfer in complex porous structures. This review provides an overview of how image analysis and processing techniques allow insight into the complex and heterogeneous porous structure of materials and explains the mechanism of heat and mass transfer in these complex porous materials in 3D and 4D observation in different directions. Accordingly, it provides interesting results related to the evaluation of microporous properties of complex porous materials including porosity, distribution and size of pores, distribution and orientation of fibers, tortuosity and mechanism of cracking, and destruction of the porous materials under mechanical tests. It also explains the mechanism of liquid transport in porous materials through 3D/4D observation thanks to image processing techniques. Therefore, this review has completed some limited knowledge in microstructural analysis and helped to understand the physical phenomena of liquid transfer in complex porous materials that were not fully exploited by experimental or simulation work. The paper also provides useful data for physical model simulation of imbibition and drying porous materials.