Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction of such molecules access to organic compounds, such as ketones has great importance in medicinal chemistry and material sciences. Hence, the coupling reaction/cyclization ring‐opening of cyclopropanols for constructing new valuable molecules in the presence of a transition metal catalyst or under metal‐free conditions is described in this context. The features of the reactions are discussed, and the mechanisms of the challenging reactions are highlighted.