Graphene nanosheets have been among the most promising candidates for a highperformance anode material to replace graphite in lithium ion batteries (LIBs). Studies in this area have mainly focused on nanostructured electrodes synthesized by graphene oxide (GO) or reduced graphene oxide (rGO) and surface modifications by a chemical treatment. Herein, we propose a cost-effective and reliable route for generating a defect-free, nanoporous graphene nanostructure (df-GNS) through the sequential insertion of pyridine into a potassium graphite intercalation compound (K-GIC). The as-prepared df-GNS preserves the intrinsic property of graphene without any crystal damage, leading to micro-/nano-porosity (microporosity: ~10–50 µm, nanoporosity: ~2–20 nm) with a significantly large specific surface area. The electrochemical performance of the df-GNS as an anode electrode was assessed and showed a notably enhanced capacity, rate capability, and cycle stability, without fading in capacity or decaying. This is because of the optimal porosity, with perfect preservation of the graphene crystal, allowing faster ion access and a high amount of electron pathways onto the electrode. Therefore, our work will be very helpful for the development of anode and cathode electrodes with higher energy and power performance requirements.