The microporous layer (MPL) is a key component of polymer electrolyte membrane fuel cells (PEM-FCs), and it is in charge of the gas and water management at the electrode-gas diffusion layer (GDL) interfaces. A MPL was prepared and coated onto two different commercial GDLs: a carbon paper (woven-non-woven (WNW)) and a carbon cloth (CC). Electrical performances of the so-obtained gas diffusion media (GDM), i.e., GDL coated with the MPL, were investigated in single cell testing (steady-state polarization curves) using a Nafion® catalyst coated membrane with a platinum loading of both for the anode and the cathode. Moreover, in order to better understand the polarization phenomena during the running of the FC, impedance spectroscopy was carried out in galvanostatic mode at different current densities. In particular, the effect of the air relative humidity (RH 100%, 80%, and 60%) was investigated, while the hydrogen was fed always fully humidified (100%). The WNW substrate has demonstrated to be superior to CC in a vast range of current densities (from open circuit voltage to ). However, at high current density, the WNW GDM has some problems in water management.