The use of electrolyte additives to form a passive solid-electrolyte interphase (SEI) at one or both electrodes is a common method for improving lithium-ion cell lifetime and performance. This work follows the chemical and electrochemical processes involved in SEI formation on graphite electrodes for two Lewis acid-base adducts, pyridine boron trifluoride (PBF) and pyridine phosphorus pentafluoride (PPF). The combination of experimental methods (electrochemistry, in situ volumetric measurements, gas chromatography, isothermal microcalorimetry, and X-ray photoelectron spectroscopy) with quantum chemistry models (density functional theory) provides new insight into the interfacial chemistry. PBF and PPF are reduced at similar to 1.3 V vs. Li/Li+ and similar to 1.4 V, respectively. This is followed by radical coupling to form 4,4'-bipyridine adducts, hydrogen transfer to ethylene carbonate solvent molecules, and reduction of the solvent to produce lithium ethyl carbonate. The reduced bipyridine adducts, Li-2(PBF)(2) and Li-2(PPF)(2), are shown to compose part of the SEI at the negative electrode surface. (C) The Author(s) 2016. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.