In this study, multilayered catalyst layers with ionomer/carbon ratio (I/C ratio) were formed using electrospray deposition (ESD). The formed catalyst layer was used as the cathode of proton exchange membrane fuel cells (PEMFCs) for polarization measurements and electrochemical impedance measurements. The structures were observed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), and the maximum power densities for the homogeneous and three-layer catalyst layers at 100% MEA humidity were 274 mW/cm2 and 312 mW/cm2, respectively, indicating the effectiveness of the multilayered catalyst layer in ESD. SEM-EDS observations showed that larger aggregates were observed at higher I/C ratios, which also affected the thickness of the layers, suggesting that multilayered I/C ratios may be accompanied by multilayered physical structures.