In this work we explore the effects of solvation, concentration, and salt chemistry on sulfone-based electrolyte performance. In graphite anode half-cells, we characterize the formation of a stable SEI which enables full utilization of the graphite electrode for the first time in an electrolyte with a sulfone as the primary solvent. In high voltage full cells, the oxidative stability of the system is confirmed by voltammetry and galvanostatic cycling measurements. Anode and cathode surface chemistry is explored extensively with XPS, and coupled with computational calculations, a mechanism for the formation and operation of both electrode/electrolyte interphases is proposed. These results suggest sulfones warrant continued consideration as a system for enabling safe, high performance, next generation Li-ion batteries.