We utilized density functional theory to examine HF generation in lithium-ion battery electrolytes from reactions between H2O and the decomposition products of three electrolyte additives: LiPF6, LiPOF4, and LiAsF6. Decomposition of these additives produces PF5, AsF5, and POF3 along with LiF precipitates. We found PF5 and AsF5 react with H2O in two sequential steps to form two HF molecules and POF3 and AsOF3, respectively. PF5 (or AsF5) complexes with H2O and undergoes ligand exchange to form HF and PF4OH (AsF4OH) with an activation barrier of 114.2 (30.5) kJ mol−1 and reaction enthalpy of 14.6 (−11.3) kJ mol−1. The ethylene carbonate (EC) electrolyte forms a Lewis acid–base complex with the PF4OH (AsF4OH) product, reducing the barrier to HF formation. Reactions of POF3 were examined and are not characterized by complexation of POF3 with H2O or EC, while PF5 and AsF5 complex favorably with H2O and EC. HF formation from POF3 occurs with a reaction enthalpy of −3.8 kJ mol−1 and a 157.7 kJ mol−1 barrier, 43.5 kJ mol−1 higher than forming HF from PF5. HF generation in electrolytes employing LiPOF4 should be significantly lower than those using LiPF6 or LiAsF6 and LiPOF4 should be further investigated as an alternative electrolyte additive.