Abstract: Rod-coil molecules with conjugated rod segments have a strong tendency to self-organize into a variety of supramolecular structures in the bulk state. This paper reports the synthesis and self-assembly behavior of coilrod-coil molecules consisting of three biphenyls linked through a vinylene unit as a conjugated rod segment and poly(ethylene oxide) (PEO) with a degree of polymerization of 12 and 17 coil segments. The self-assembling behavior of these materials, which was investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD), revealed these molecules to spontaneously self-organize into a 3-D hexagonally perforated layer (HPL) structure and a 2-D rectangular or a oblique columnar structure in the crystalline and liquid crystalline phases, respectively.