Elementary processes of electro mass transfer in the nanocomposite polymer electrolyte system by pulse field gradient, spin echo NMR spectroscopy and the high-resolution NMR method together with electrochemical impedance spectroscopy are examined. The new nanocomposite polymer gel electrolytes consisted of polyethylene glycol diacrylate (PEGDA), salt LiBF4and 1—ethyl—3—methylimidazolium tetrafluoroborate (EMIBF4) and SiO2nanoparticles. Kinetics of the PEGDA matrix formation was studied by isothermal calorimetry. The flexible polymer–ionic liquid films were studied by IRFT spectroscopy, differential scanning calorimetry and temperature gravimetric analysis. The total conductivity in these systems was about 10−4S cm−1(−40 °C), 10−3S cm−1(25 °C) and 10−2S cm−1(100 °C). The method of quantum-chemical modeling of the interaction of SiO2nanoparticles with ions showed the advantage of the mixed adsorption process, in which a negatively charged surface layer is formed from Li+BF4—ions on silicon dioxide particles and then from ions of the ionic liquid EMI+BF4−. These electrolytes are promising for use both in lithium power sources and in supercapacitors. The paper shows preliminary tests of a lithium cell with an organic electrode based on a pentaazapentacene derivative for 110 charge–discharge cycles.