In this report, we show that the microstructures of hydrogen-bonded side-chain liquid-crystalline block copolymers can be rapidly aligned in an alternating current (AC) electric field at temperatures below the order-disorder transition but above the glass transition. The structures and their orientation were measured in real time with synchrotron X-ray scattering. Incorporation of mesogenic groups with marked dipolar properties is a key element in this process. A mechanism related to the dissociation of hydrogen bonds is proposed to account for the fast orientation switching of the hydrogen-bonded blends.