The regio-/stereoselective synthesis of vinyl cyclobutanols from alkynyl cyclobutanols is demonstrated. Here, selective C-C bond activation of the cyclopropyl alcohol ring has been achieved in the presence of the cyclobutanol ring. The KIE experiments indicated the noninvolvement of the O-H oxidative addition step in the rate-determining step. Further, the applicability of these vinyl cyclobutanols for the synthesis of 1,4-diketones and 1,6-diketone is demonstrated.