Abstract: Epoxide ring opening is a frequently required transformation in Organic Synthesis. In this paper we describe the application of NbCl 5 for this purpose using three different substrates. Chlorohydrins, 1, 2-diols, products containing solvent residues as well as rearrangement products are obtained, depending on both the substrate structure and reaction conditions. Rationalizations to account for some of the results are suggested.