Materials that respond rapidly and reversibly to external stimuli currently stand among the top choices as actuators for real‐world applications. Here, a series of programmable actuators fabricated as single‐ or bilayer elements is described that can reversibly respond to minute concentrations of acetone vapors. By using templates, microchannel structures are replicated onto the surface of two highly elastic polymers, polyvinylidene fluoride (PVDF) and polyvinyl alcohol, to induce chiral coiling upon exposure to acetone vapors. The vapomechanical coiling is reversible and can be conducted repeatedly over 100 times without apparent fatigue. If they are immersed in liquid acetone, the actuators are saturated with the solvent and temporarily lose their motility but regain their shape and activity within seconds after the solvent evaporates. The desorption of acetone from the PVDF layer is four times faster than its adsorption, and the actuator composed of a single PVDF layer maintains its ability to move over an acetone‐soaked filter paper even after several days. The controllable and reproducible sensing capability of this smart material can be utilized for actuating dynamic elements in soft robotics.