A comprehensive understanding of the solid–electrolyte interphase (SEI) composition is crucial to developing high-energy batteries based on lithium metal anodes. A particularly contentious issue concerns the presence of LiH in the SEI. Here we report on the use of synchrotron-based X-ray diffraction and pair distribution function analysis to identify and differentiate two elusive components, LiH and LiF, in the SEI of lithium metal anodes. LiH is identified as a component of the SEI in high abundance, and the possibility of its misidentification as LiF in the literature is discussed. LiF in the SEI is found to have different structural features from LiF in the bulk phase, including a larger lattice parameter and a smaller grain size (<3 nm). These characteristics favour Li+ transport and explain why an ionic insulator, like LiF, has been found to be a favoured component for the SEI. Finally, pair distribution function analysis reveals key amorphous components in the SEI. X-ray diffraction and Rietveld refinement analysis confirm the presence of LiH in the solid–electrolyte interphase of lithium metal anodes.