Synthetic studies on chlorosulfolipids, an intriguing class of freshwater microalgae‐derived natural products, have already unearthed some of their enigmatic biological and chemical properties. Numerous syntheses have showcased diverse strategies, which include unanticipated anchimeric assistance by chlorides in openings of allylic epoxides. Yet, despite the extensive work that has been documented, this natural product class harbors additional surprises in store. Herein we report one such discovery, i. e. a [1,3]‐sigmatropic shift of an allylic chloride.