The plasma modification of the polypropylene (PP) membrane as a separator in lithium-ion battery (LIB) has been reported in this paper. Specifically, a commercial PP separator was modified by an atmospheric pressure glow discharge plasma jet (APGD-PJ) with the acrylic acid (AA) monomer. The morphology, electrolyte uptake and retention, the pore size distribution, and the electrochemical properties of the modified PP separator were analyzed. The experimental results indicate that the AA polymer (PAA) was uniformly coated on the surface of the PP membrane, and the contact angle of modified PP was reduced from 112° to 39° using He/O2/AA plasma and the electrolyte uptake of the modified PP separator increased to above 300% of the value of the unmodified one. Compared with the original PP, the cells assembled with the PP separator modified with Ar/O2/AA or He/O2/AA plasma showed higher capacities and better C-rate capacity. The excellent performances of assembled LIB endow the APDG-PJ as a promising protocol for modifying polyolefin separators for LIB applications.