For its low redox potential (−3.04 V vs. SHE) and the high theoretical specific capacity (3860 mA h g−1), lithium metal is regarded as one of the most promising anode materials for next-generation batteries. However, the poor cycling performances and serious safety hazards caused by the inhomogeneous lithium deposition severely hinder the practical applications of Li metal batteries. Here, we introduce 3-D carbon materials which are subsequently in-situ transformed into LiC6 as electrode scaffold. Such lithiophilic 3-D structure with a high specific surface area enables dendrite-free deposition of Li metal, resulting in a high coulombic efficiency up to 97% after 300 cycles. We propose that besides 3-D structure, LiC6 intermediate may be responsible for the dendrite-free growth of Li, offering a potential new strategy to design high performance anodes for Li metal batteries.