Ethylene carbonate (EC) is the most widely used electrolyte solvent in lithium ion batteries, but it fails to form a stable passivation layer on materials such as Si and Li metal, which will enable the long-term cycling of the next-generation high-capacity lithium ion batteries containing these anode materials. High concentrations of soluble degradation products are detected in the electrolyte after prolonged cycling, but the chemical structures of these species remain unclear. Here, we used 1D, 2D, and diffusion NMR techniques combined with mass spectrometry to analyze electrolyte-containing 13C-labeled EC, and we report on the formation of a series of linear oligomers consisting of ethylene oxide and carbonate fragments with methoxide end groups as the major soluble degradation products of EC. Oligomers with methoxide terminals are likely to have weak interaction toward the electrode; thus, they easily detach from the electrode and are unable to passivate the surface, which may explain the origin of the capacity fade for high-capacity Si-based or Li metal anodes.