Lithium metal anodes potentially offer an ultrahigh energy density for Li-ion batteries. In article number 1701482, Nae-Lih Wu and co-workers report a new strategy for developing a dendrite-free Li anode technology. A high-polarity β-phase poly(vinylidene difluoride) thin coating with an electronegative F-rich interface on either copper or lithium metal substrates is demonstrated to enable uniform massive lithium deposition/stripping and high cycle stability.