The large-scale adoption of fuel cells system for sustainable power generation will require the combined use of both multidimensional models and of dedicated testing techniques, in order to evolve the current technology beyond its present status. This requires an unprecedented understanding of concurrent and interacting fluid dynamics, material and electrochemical processes. In this review article, Polymer Electrolyte Membrane Fuel Cells (PEMFC) are analysed. In the first part, the most common approaches for multi-phase/multi-physics modelling are presented in their governing equations, inherent limitations and accurate materials characterisation for diffusion layers, membrane and catalyst layers. This provides a thorough overview of key aspects to be included in multidimensional CFD models. In the second part, advanced diagnostic techniques are surveyed, indicating testing practices to accurately characterise the cell operation. These can be used to validate models, complementing the conventional observation of the current−voltage curve with key operating parameters, thus defining a joint modelling/testing environment. The two sections complement each other in portraying a unified framework of interrelated physical/chemical processes, laying the foundation of a robust and complete understanding of PEMFC. This is needed to advance the current technology and to consciously use the ever-growing availability of computational resources in the next future.