We demonstrate that the supramolecular structure can be formed through the fibrous self-assembly of the polyfluorene-based polymer F8BT in liquid crystal (LC) 5CB. With the utility of alignment layer, the F8BT molecules can be aligned and formed oriented polymer network. We found that the presence of oriented polymer network makes twisted nematic LC exhibit excellent electro-optical properties (EO) of driving voltage reduction and EO bump peak elimination. The polyfluorene-based supramolecular structure provides the function of stabilizing LC molecules. We consider this functional self-assembled network has potential to apply in various devices for the ability of improving performance in operating property.