Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0M LiPF6 in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO2Li, ROLi, Li2CO3, etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes.