Although chiral oxacycles frameworks are present in a wide range of natural products and bioactive molecules, however, very few examples enabling the direct synthesis of these chiral cyclic ethers are available. We have demonstrated a highly enantioselective cycloetherification strategy for the straightforward synthesis of enantio-enriched cyclic ethers using a cation-binding Song’s oligoEG catalyst and KF as the base. A wide range of ε, ζ and η-hydroxy-α,β-unsaturated ketones were cyclized to the corresponding chiral cyclic ethers mediated by low catalyst loading of (R)-cat. This approach provides a new catalytic system for oxa-heterocycle synthesis, which would be useful for constructing a library of naturally occurring similar scaffolds. Initial simultaneous activation of potassium fluoride and the carbonyl group of α,β-unsaturated ketones by the catalyst and subsequent attack of the hydroxy group in an oxa-Michael fashion generated the requisite chiral oxacycle. A densely confined chiral space is formed in situ by the cation-binding catalyst through incorporation of potassium salt, which simultaneously activates both reaction centers in n-hydroxy-α,β-unsaturated ketones resulting in enhanced reactivity and efficient transfer of stereochemical information.