In an effort to develop low-flammability electrolytes for a new generation of Li-ion batteries, we have evaluated physical and electrochemical properties of electrolytes with two novel phosphazene additives. We have studied performance quantities including conductivity, viscosity, flash point, and electrochemical window of electrolytes as well as formation of solid electrolyte interphase (SEI) films. In the course of study, the necessity for a simple method of SEI characterization was realized. Therefore, a new method and new criteria were developed and validated on 10 variations of electrolyte/electrode substrates. Based on the summation of determined physical and electrochemical properties of phosphazene-based electrolytes, one structure of phosphazene compound was found better than the other. This capability helps to direct our further synthetic work in phosphazene chemistry.