The ring-opening of cyclopropanols is one of the most active areas of research and it has been well documented in recent years owing to subsequent coupling with various partners, thus providing the facile syntheses of a large number of multifunctional compounds that may otherwise be difficult to access. Evidently, the useful cascade reaction requires easy access to diversely functionalized cyclopropanol substrates. However, developments in the construction of cyclopropanols have not received adequate attention. Herein, recent reports on the formation of cyclopropanols are summarized, and the highly stereoselective production of new promising substrates for the cyclopropanol ring-opening/cross-coupling reactions are introduced and improved syntheses of known cyclopropanols are depicted. This review may facilitate more interesting applications of the cyclopropanol ring-opening/coupling reaction in the synthesis of pharmaceutical compounds, natural products, and structurally more diversified organic synthetic intermediates.