Abstract A photopromoted Pd‐catalyzed Heck reaction of gem ‐difluorocyclopropyl bromides (DFCBs) with styrenes to deliver vinyl gem ‐difluorinated cyclopropanes (VDFCs) under mild conditions has been developed. The reaction demonstrates good functional group compatibility while providing high E/Z ratio of the products. Furthermore, the desired VDFCs can be easily transformed into fluorinated cyclic/acyclic architectures, which may broaden its applications in organic synthesis.