A nanocomposite built of the hydrogen-bonded (HB) dimer liquid crystal 4-heptyloxybenzoic acid (7OBA) and Graphene oxide (GO) exhibiting a cascade of phase transitions and phases not typical for pristine 7OBA, was investigated by optical polarization microtexture analysis and Raman spectroscopy. We use the 7OBA/GO nanocomposite beacause of the effective functionalizing properties of GO to study the generation and development of the ferroelectric smectic CG phase in its bi-tilted configuration. For the appearance of the CG phase with its substructures we propose an explanation based on the HB formation between 7OBA dimers in closed and open conformations and the GO sheets, aided by the π–π interaction with graphene hexagons which are free from functional groups. We propose molecular and macroscopic models for the substructures CGcl and CGln and indicate their triclinic C1 symmetry, characterized by a polar vector directed oblique to the layers. This confirms that the bi-tilted CG and its substructures are ferroelectric in the bulk similarly to solid ferroelectrics, thus showing potential as material for controllable photonic functional devices.