Rational molecular design and processing, enabling large-area molecular ordering, are important for creating high-performance organic materials and devices. We show that, upon one-step hot-pressing with uniaxially stretched Teflon sheets, a polymer brush carrying azobenzene-containing mesogenic side chains self-assembles into a freestanding film, where the polymer backbone aligns homeotropically to the film plane and the side chains align horizontally. Such an ordered structure forms through translation of a one-dimensional molecular order of the Teflon sheet and propagates from the interface macroscopically on both sides of the film. The resultant wide-area bimorph configuration allows the polymer film to bend rapidly and reversibly when the azobenzene units are photoisomerized. The combination of polymer brushes with hot-pressing and Teflon sheets provides many possibilities in designing functional soft materials.