A series of supramolecular liquid crystalline block copolymers (SLCBCPs) were prepared by hydrogen-bonding interaction between poly(dimethylsiloxane)-b-poly(2-vinyl-terephthalic acid) (PDMS-b-PM1H) and [4-(4'-hexyloxy)styryl]-pyridine (NC6). PDMS-b-PM1H serves as the hydrogen-bonding donor and NC6 as the hydrogen-bonding acceptor. The SLCBCPs are obtained by mixing the hydrogen-bonding acceptor and donor in pyridine. Through increasing the molar ratio of pyridine to carboxyl, the SLCBCPs can transform from coil-coil block copolymers (BCPs) to rod-coil ones. When the ratio of pyridine to carboxylic acid is 0.50 or lower, the SLCBCPs are coil-coil-like. However, when the ratio exceeds 0.50, the SLCBCPs behave like rod-coil BCPs because the supramolecular block PM1H(NC6) exhibits liquid crystalline (LC) behavior owing to the "jacketing" effect. Small-angle X-ray scattering and transmission electron microscopy experiments were employed to characterize the microphase-separated nanostructures of the SLCBCPs. Interestingly, when the weight fraction of the supramolecular block PM1H(NC6) ranges from 51% to 92%, hexagonally packed cylinders (HEX) are always obtained. Compared to conventional BCPs, the SLCBCPs prepared can more easily self-assemble into the HEX nano-structures that may potentially serve as nano templates and porous materials after selective etching. In addition, the SLCBCPs can form hierarchically ordered nano structures, including the HEX nano-structure of the SLCBCP and the LC phase of the supramolecular block.