In this study, novel asymmetric cycloetherification via the kinetic resolution of secondary or tertiary alcohols using chiral phosphoric acid catalysts was developed, affording tetrahydropyrans (THPs) with two stereogenic centers. The cyclization of the recovered optically active alcohols afforded other stereoisomers of THPs. These protocols offer efficient synthetic routes to various optically active THP derivatives, which are important structures found in a range of biologically active agents.