A C2-symmeric binaphthyl framework bearing phenanthrene as the emitter exhibited circularly polarised luminescence (CPL) in dilute solutions. The CPL and circular dichroism signs of the luminophores were altered by solvents (chloroform, methanol, acetonitrile, and dimethylformamide). DFT and TD-DFT calculations indicated that the dihedral angle between the phenanthrene and naphthyl rings was responsible for the apparent sign inversion. The role of solvent molecules in the ground and photoexcited states was discussed based on Hansen solubility parameters (δ, δd, δp and δh).