The cycling performance of LiPF4(C2O4) electrolyte is compared with LiPF6 electrolyte in the presence of several different electrode materials. The cycling of MCMB/LiNi1/3Co1/3Mn1/3O2 and natural graphite/LiFePO4 cells provides very similar performance for both electrolytes. However, MCMB/LiMn2O4 cells have a lower initial reversible capacity with LiPF4(C2O4) electrolytes. A detailed analysis of the surface films on both the cathode and the anode via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) was conducted. The performance differences are attributed to the anode as opposed to the cathode.