Dendrite growth and low coulombic efficiency are two major factors that limit the utilization of Li metal electrodes in future generations of high-energy-density rechargeable batteries. This article reports the first study on metal-organic framework (MOF) materials for boosting the electrochemical performance of Li metal electrodes and demonstrates the power of molecular-structure functionalization for realizing desirable ion transport and Li metal nucleation and growth. We show that dendrite-free dense Li deposition and stable Li plating/stripping cycling with high coulombic efficiency are enabled by modifying a commercial polypropylene separator with a titanium-based MOF (NH2-MIL-125(Ti)) material. The NH2-MIL-125(Ti)-coated-separator renders Li|Cu cells that can run for over 200 cycles at 1 mA cm-2-1 mA h cm-2 with average coulombic efficiency of 98.5% and Li|Li symmetric cells that can be cycled at 1 mA cm-2-1 mA h cm-2 for more than 1200 h without short circuiting. The superior cycling stability is attributed to the amine substituents in the NH2-MIL-125(Ti) structure which induce increased Li+ transference numbers and uniform and dense early-stage Li deposition.