Polymer electrolyte membrane fuel cells (PEMFCs) have been developed as an efficient and eco-friendly energy-conversion device for distributed power generation, transportation, and stationary uses. Notwithstanding the advances in PEMFC technology, durability and cost remain the two main challenges to be overcome for their large-scale commercialization. In this contest, the polyaromatic membranes based on sulphonated polyetheretherketone (sPEEK), due to its properties such as high thermal and chemical stability, excellent mechanical properties, good proton conductivity, can be considered as an alternative and good candidate to conventional membrane. In order to stabilize the membranes maintaining a proton path for the conduction mechanism and improving the characteristics of the sPEEK material, opportunely selected porphyrins able to specifically interact with the polymeric matrix, were added [1, 2]. Composite membranes based on s-PEEK and different percentages of porphyrins were developed by doctor blade technique. To verify the occurred insertion and interaction between the polymeric matrix and porphyrin, physico-chemical characterizations in terms of UV-Vis and Fluorescence emission, ion exchange capacity, water retention, dimensional variations and swelling, structural and morphological analyses were carried out. Moreover, proton conductivity measurements were performed to understand the influence of the interactions on the proton transport mechanism. Finally, electrochemical tests in a single cell configuration PEFC fed by hydrogen and air were performed on the developed membranes to verify the performance in the selected operative conditions. It was found that the insertion of porphyrins in the polymeric matrix influences its characteristics as a function of the amount introduced, permitting to operate in a wide range of operative conditions such as temperatures and relative humidities.