Gold-catalyzed Prins-type cyclizations are interesting strategies for synthesizing complex molecules with excellent diastereoselectivity. We developed a novel and efficient system for such processes (13 examples, ≤89% yield) and reported the first enantioselective version of a gold-catalyzed Prins-type cyclization using a new chiral TADDOL-based Au(I) phosphonite complex. After crystallization, highly enantiomerically enriched products were obtained with >99% ee.