The palladium-catalyzed telomerisation of butadiene with glycerol has been studied under aqueous biphasic conditions both in the presence of a liquid phase of butadiene and under gaseous atmosphere of butadiene. In this last case, gaseous butadiene was continuously added during the whole reaction time keeping constant its pressure. Most of the products formed have been fully characterized. The influence of various experimental parameters has been checked with the aim to obtain high activities and selectivities either into mono-, di- or tritelomers. (c) 2010 Elsevier B.V. All rights reserved.