Graphitic carbon is currently considered the state-of-the-art material for the negative electrode in lithium ion cells, mainly due to its high reversibility and low operating potential. However, carbon anodes exhibit mediocre charge/ discharge rate performance, which contributes to severe transport-induced surface structural damage upon prolonged cycling and limits the lifetime of the cell. Lithium bulk diffusion in graphitic carbon is not yet completely understood, partly due to the complexity of measuring bulk transport properties in finite-sized nonisotropic particles. To solve this problem for graphite, we use the DevanathanStachurski electrochemical methodology combined with ab initio computations to deconvolute and quantify the mechanism of lithium ion diffusion in highly oriented pyrolytic graphite (HOPG). The results reveal inherent high lithium ion diffusivity in the direction parallel to the graphene plane (∼10-7 -10-6 cm2 s -1 ), as compared to sluggish lithium ion transport along grain boundaries (∼10-11 cm2 s -1 ), indicating the possibility of rational design of carbonaceous materials and composite electrodes with very high rate capability.