To find a novel high-performance anode material for lithium-ion batteries, a new form of carbon characterized by highly crimped and crystalline nanofibrillar microtextures was produced by heat treating polyacrylonitrile/FeCl3 hybrid precursor and subsequent thermal annealing under hydrogen gas. This form of carbon exhibits a rechargeable capacity of ∼630mAh/g, which is superior to that of graphite, with a Coulomb efficiency of ∼70%. Further, the new form of carbon was found to exhibit an efficiency of lithium ion insertion/extraction of ∼100% in the voltage range from 0.06 to 0.80V, with a capacity of ∼400mAh/g. We speculate that this excellent capacity is due to the characteristic structure of this form of carbon, i.e. its highly entangled web-like hyperstructure consisting of highly crimped and crystalline nanofibrillar microtextures, which enables good permeation and has high resilience to volume deformation during the insertion/extraction of Li ions.