ε-Fe2C has been predicted promising for low-temperature Fischer–Tropsch synthesis (LTFTS) targeting at liquid fuel production.[1] However, directional carbidation of metallic iron to ε-Fe2C is greatly challenged by kinetic hindrances.[2] Here we show how rapidly quenched skeletal iron (RQ Fe) featuring nanocrystalline dimension, low coordination number, and expanded lattice can solve this problem.