The effective use of ring strain has been applied to considerable advantage for the construction of complex systems. The focus here is directed towards cyclopropanes as building blocks for organic synthesis. Although thermodynamics should take the side of synthetic chemists, only a specific substitution pattern at the cyclopropane ring allows for particularly mild, efficient, and selective transformations. The required decrease in the activation barrier is achieved by the combined effects of vicinal electron‐donating and electron‐accepting moieties. This Review highlights the appropriate tools for successfully employing donor–acceptor cyclopropanes in ring‐opening reactions, cycloadditions, and rearrangements. Tug‐of‐war on cyclopropanes: Even though donor–acceptor‐substituted cyclopropanes were already investigated 30 years ago, the last few years have brought about a renaissance in their chemistry. This Review highlights the most recent developments regarding ring opening, cycloadditions, and ring enlargement.