New ternary graphite intercalation compounds (GICs) containing Na+ and linear alkylamines (Na-Cx-GIC) are reported. The following new GICs with indicated stages and intercalate arrangements are obtained: stage 1, monolayer (C3, C4); stage 1, bilayer (C6, C8); and stage 2 bilayer (C12, C14). Two features new to donor-type GICs found are (i) an intercalate bilayer arrangement with guest alkyl chains parallel to encasing graphene layers, and (ii) the transition from an intercalate bilayer to monolayer arrangement upon evacuation for C6. Although there are many reports on the intercalation of short, medium, and long-chain alkylamines in layered hosts, this is the first example of a homologous compound series for GICs. The products obtained are characterized using powder X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry.