Lithium–graphite intercalation compounds were synthesized by intercalating various amount of lithium into graphite electrochemically. X-ray diffraction was measured and the layered structures of the lithium–graphite intercalation compounds (Li-GICs) were precisely analyzed by one-dimensional Rietveld method. The layered structures for stage 1, stage 2, stage 2L, stage 3, and stage 4 were verified precisely. The spacings both between graphene layers with a lithium layer intercalated and between graphene layers with no lithium layer intercalated were obtained. The changes of these values were discussed based on the structure of stage compounds.