A new approach accompanied by superstructural frustration is reported. By attaching a cholesterol moiety directly to the central bent-core system it displayed exotic BPIII, BPII/I, Ncyb*, TGBA, SmAPA, SmA and SmX phases as shown by X-ray scattering results. While higher homologues of the series exhibited spontaneous formation of polar order (Ps ∼ 61 nC cm-2) upon applied voltage, the lower homologues showed thermochromic behaviour which can also be trapped via temperature quenching.