In recent years, reaction of inexpensive and abundantly available alcohols (C–OH) with unactivated nucleophilic coupling partners (C–H), leading to the construction of the C–C bond, has emerged as one of the vital strategies since it is an atom-economical and environmentally benign approach with water as the by-product. Various transition metal-catalyzed or metal-free approaches for the direct dehydrative coupling employing the C–OH bond (including in situ activation) have recently been devised. This review article aims to highlight advances in such waste-free C–C bond forming dehydrative strategies.