A Lewis-base-catalyzed three-component electrophilic thiofunctionalization of cyclopropene with phenol is developed to furnish various trisubstituted chromanes in high trans-diasteroselectivity. This metal-free protocol is easy to scale-up, offers a unique 2,2,3-substitution pattern, and delivers chromanes with diversified core substitution patterns. The unprecedented tolerance of strong electron-withdrawing substituents at the phenol renders the protocol indispensable to access the otherwise inaccessible chromane chemical space that is important for medicinal chemistry campaigns.