In this work, 3D-conductive supramolecular gel and derivates were synthesized and the performance of lithium storage were explored. In sol or gel state of iron-based metal-organic gel (Fe-MOG), the redox reaction of Fe3+ will generate free radicals which can catalyze the polymerization of pyrrole. Meanwhile, the conductive polymer could be more uniformly and closely coated on the internal structure of Fe-MOG. Systematic electrochemical analysis demonstrated that 3D-conductive supramolecular gel anode performed a stable reversible specific capacity of 1304.9 mAh g−1 at the current density of 0.1 A g−1, and outstanding cycle performance with high reversible specific capacity of 824.5 mAh g−1 at the current density of 0.4 A g−1 after 300 cycles and 422.3 mAh g−1 at the current density of 2 A g−1 after 100 cycles. At the same time, supramolecular gel-derived N-doped Fe–C could also show excellent performance of lithium storage as a novel carbon material, demonstrating that 3D-conductive supramolecular gel has a broad application prospect in the field of lithium-ion batteries (LIBs).