Magnetoelectric multiferroic materials have exhibited unique advantages in low-power and high-density information storage as they can simultaneously display ferroelectricity and ferromagnetism. However, research on how to construct air-stable high-performance magnetoelectric (ME) single-molecule magnets (SMMs) is nonexistent. Herein, by introducing homochirality meanwhile reducing molecular symmetry, two double-decker Dy(III) enantiomers adopting the polar space group P2 1 with excellent thermal stability were obtained. They display zero field SMM behavior with anisotropy barrier (U eff