Vinylene carbonate (VC) was tested as an additive to electrolyte solutions for Li-ion batteries. For the model electrodes, synthetic graphite was chosen as the anode material, while LiMn2O4 spinel and LiNiO2 were chosen as the cathode materials. The test solution was 1 M LiAsF6 in a 1:1 mixture of ethylene and dimethyl carbonates (EC–DMC). Cyclic voltammetry (CV), chronopotentiometry, impedance spectroscopy, electrochemical quartz crystal microbalance (EQCM), FTIR and X-ray photoelectron spectroscopies have been used in this study. It was found that VC is a reactive additive that reacts on both the anode and the cathode surfaces. The influence of this additive on the behavior of Li–graphite anodes is very positive, since it improves their cyclability, especially at elevated temperatures, and reduces the irreversible capacity. The spectroscopic studies indicate that VC polymerizes on the lithiated graphite surfaces, thus forming poly alkyl Li-carbonate species that suppress both solvent and salt anion reduction. The presence of VC in solutions reduces the impedance of the LiMn2O4 and LiNiO2 cathodes at room temperature. However, we have not yet found any pronounced impact of VC on the cycling behavior of the cathodes, either at room temperature or at elevated temperatures. Thus, VC can be considered as a desirable additive for the anode side in Li-ion batteries, one which has no adverse effect on the cathode side.