Functionally gradient polymer electrolytes were prepared from 2- [2-(2-ethoxyethoxy)ethoxy] ethoxydimethylvinylsilane (EDVS) containing 10 wt% LiCF3SO3 by a plasma polymerization technique from liquid phase. The polymer electrolytes were characterized by FT-IR, X-ray photoelectron spectroscopy, and the ionic conductivity measurements. From the LR spectra of EDVS plasma polymer electrolytes, the characteristic peaks for olefin groups disappeared but the spectra were similar to that of EDVS monomer, indicating that the polymerization occurs mainly by a chain propagation. The ionic conductivity increased from surface to bulk of the plasma polymer, that is, functionally gradient polymer electrolytes were prepared.