The intermolecular cyclopropanation of 2‐aryl and 2‐styryl substituted ethenesulfonyl fluorides with active cyano‐containing methylenecompounds was described. This reaction proceeds via carbon‐sulfur bond cleavage under metal‐free conditions in up to 99% yield, affording a variety of nitrile‐substituted cyclopropanes with high diastereoselectivity.