Intercalation of very long molecules into the structure of multi-layered graphene oxide (GO) was studied using example of 1-hexadecanol (C16), an alcohol molecule with 16 carbon atoms. Brodie graphite oxide (BGO) immersed in excess of liquid C16 just above the melting point shows expansion of c-unit cell parameter from ∼6 Å to ∼48.76 Å forming a structure with two densely packed layers of C16 molecules in a perpendicular orientation relative to the GO planes (α-phase). Heating of the BGO-C16 α-phase in excess of C16 melt results in reversible phase transition into β-phase at 336–342K. The β-phase shows much smaller unit cell parameter of 29.83 Å (363K). Analysis of data obtained using vacuum-driven evaporation of C16 from the β-phase provides evidence for structure of β-phase consisting of five layers of C16 molecules in parallel to GO plane orientation. Therefore, the transition from α-to β-phase corresponds to change in orientation C16 molecules from perpendicular to parallel relative to GO planes and decrease in the amount of intercalated solvent. Cooling of the β-phase in absence of C16 melt is found to result in the formation of γ-phase with inter-layer distance of ∼26.5 Å corresponding to one layer of C16 molecules intercalated perpendicularly relative to the GO planes. Structures with one and two layers of C16 molecules parallel to GO planes were identified in samples with rather small initial loading of C16. Surprisingly rich variety of structures revealed in the BGO-C16 system provides opportunities to create materials with precisely controlled GO inter-layer distance.