The applicability of Na-ion batteries is contingent on breakthroughs in alternative electrode materials that have high capacities and which are economically viable. Unfortunately, conventional graphite anodes for Li-ion battery systems do not allow Na-ion accommodation into their interlayer space owing to the large ionic radius and low stabilizing energy of Na in graphite. Here, we suggest a promising strategy for significantly increasing Na capacity by expanding the axial slab space of graphite. We successfully synthesized reconstructed graphite materials via self-assembly of negative graphite oxide (GO) flakes and Al cation (positive) pillars and by subsequent chemical reaction of the obtained Al-GO materials. Al pillars, atomically distributed in graphite interlayers, can extend the slab space by up to ∼7 Å, which is a 2-fold interlayer distance of pristine graphite. An exceptionally high capacity of 780 mAh/g is demonstrated for reconstructed graphite anodes with Al pillars, compared with rGO materials (210 mAh/g). We investigated the electrochemical reaction mechanism and structural changes associated with discharge and charge to emphasize the benefit of using reconstructed graphite as anodes in Na-ion batteries. Our strategy of modifying the interlayer distance by introducing metallic pillars between the layers can help address the low capacity of carbonaceous anodes.