We have found that certain combinations of specific additives show a very interesting behavior in Li-ion batteries. During the course of investigating further improvements in the performance of the triple-bonded compounds, which we very recently reported, a novel and unique effect of an additive combination was observed. The combination of the triple-bonded compounds and the double-bonded compounds has proven to show a much improved battery performance, especially in cycleability and gas evolution than the case when they are singly used. Especially, the synergetic effect of propargyl methanesulfonate and vinylene carbonate is remarkable. To clarify the synergetic effect, the electrochemical properties of the additives and the electrode analyses were investigated. It is assumed that the higher battery performance of the combination effect resulted not only from the thin and dense SEI on the negative electrode but also from the positive electrode surface co-polymerized film produced by the synergetic decomposition of the additives. We suggest that the keys for producing the synergetic functions are (1) a structural difference in the unsaturated moiety, and (2) a greater difference in the reduction potential.