Lithium metal has been considered as the most promising anode material for rechargeable Li batteries because of its high theoretical specific capacity. However, significant challenges, including Li dendrite growth, inferior rate and low Coulombic efficiency (CE), have prevented their practical applications. Here we report a facile strategy to improve the anode performance by decorating the Cu foil substrate with a nanoporous polyether sulfone (PES) film. After employing the PES layer, the Li plating/stripping stability has been dramatically improved to more than 800 h and the Coulombic efficiency kept higher than 99% even after 200 cycles. Moreover, the voltage gap between Li stripping and plating experienced no obvious changes after long time cycles. The Li dendrite formation have been effectively suppressed after PES coating. The PES coating layer also greatly improved the Li metal stability in ambient air.