Reformulation of electrolyte systems and improvement of separator wettability are vital to electrochemical performances of rechargeable lithium (Li) metal batteries, especially for suppressing Li dendrites. In this work we report a bifunctional electrolyte additive that improves separator wettability and suppresses Li dendrite growth in Li metal batteries. A triblock polyether (Pluronic P123) is added as an additive into a commonly used carbonate-based electrolyte. It is found that addition of 0.2–1% (by weight) P123 into the electrolyte can effectively enhance the wettability of polyethylene separator. More importantly, the adsorption of P123 on Li metal surface can act as an artificial solid electrolyte interphase layer and suppress the growth of Li dendrites. A smooth and dendrite-free Li morphology can be achieved in the electrolyte with 0.2% P123. The Li||Li symmetric cells with the 0.2% P123-containing electrolyte exhibit a relatively long cycling stability at high current densities of 1.0 and 3.0 mA cm−2.