Electrochemical impedance spectroscopy is an important tool for fuel-cell analysis and monitoring. This study focuses on the low-AC frequencies (2–0.1 Hz) to show that the thickness of the catalyst layer significantly influences the overall resistance of the cell. By combining known models, a new equivalent circuit model was generated. The new model is able to simulate the impedance signal in the complete frequency spectrum of 105–10−2 Hz, usually used in experimental work on polymer electrolyte fuel cells (PEMFCs). The model was compared with experimental data and to an older model from the literature for verification. The electrochemical impedance spectra recorded on different MEAs with cathode catalyst layer thicknesses of approx. 5 and 12 µm show the appearance of a third semicircle in the low-frequency region that scales with current density. It has been shown that the ohmic resistance contribution (Rmt) of this third semicircle increases with the catalyst layer’s thickness. Furthermore, the electrolyte resistance is shown to decrease with increasing catalyst-layer thickness. The cause of this phenomenon was identified to be increased water retention by thicker catalyst layers.