The hydrophilic surface modification of the polymeric separator is achieved by low-pressure 13.56 MHz radio-frequency Ar and He gas plasma treatments. The changes in surface hydrophilicity and surface free energy were examined by static contact angle analysis. The static water contact angle of the plasma-modified polymeric separator particularly decreased with the increase in treatment time. An obvious increase in the surface energy of polymeric separators owing to the crosslinking by activated species of inert gases effect of monatomic-gas-plasma treatments was also observed. Optical emission spectroscopy was carried out to analyze the chemical species generated after Ar and He gas plasma treatments. The variations in the surface morphology and chemical structure of the polymeric separators were confirmed by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS) measurements. XPS analysis showed significantly higher surface concentrations of oxygen functional groups for monatomic-gas-plasma-modified polymeric separator surfaces than for the unmodified polymeric separator surface. The experimental results show the important role of chemical species in the interaction between Ar and He gas plasmas and the polymeric separator surface, which can be controlled by surface modification to tailor the hydrophilicity of the polymeric separator.