Polymer Electrolyte Fuel Cells (PEFC) are electro-chemical energy conversion devices capable of providing sustainable transport, stationary and portable solutions, owing to their high-power density and fast start-up time. However, water management remains one of the largest barriers limiting fuel cell efficiency and the wide scale deployment of PEFC. The microporous layer (MPL) of PEFC is widely acknowledged as a crucial, performance enhancing component; increasing cell efficiency and durability, largely by the improved management of liquid water and two-phase flow.The purpose of this research is to develop a greater understanding of how composition affects MPL microstructure and morphology, and ultimately identifying strategies to improve fuel cell efficiency. Here we present the fabrication and characterisation of novel MPLs produced from graphene-based materials. Graphene-based materials are a highly promising MPL material, due to their unique physical structure and their excellent electric and thermal conductivity. MPLs were produced from graphene-based materials and compared to conventional carbon black. The graphene-based materials studied were; graphene foam, derived from pyrolysis of sodium ethoxide (GF); graphene nanoplatelets (GN); and multi-wall carbon nanotubes (CNT). The synergetic effect of carbons with different aspects was also studied by the fabrication of composite MPLs mixed with conventional carbon black. Analysis of the performance enhancement and water management capabilities of the MPLs was conducted through microstructural and physical ex-situ characterisation, and polarisation measurements at 100% and 20% relative humidity (RH).Detailed analysis of the physical characteristics, morphology and microstructure provides an insight into how MPL architecture can be optimised to facilitate mass transport and negate flooding issues whilst maintaining membrane hydration. Thus, graphene-based materials hold the potential to optimise the MPL’s ability for reactant, heat and electron transport, over a range of operating conditions, and so improving overall cell efficiency.