The telomerization of butadiene with solketal (1,2-isopropylideneglycerol) in the presence of palladium complexes has been studied under aqueous biphasic conditions. This reaction followed by deprotection in acid medium leads to monooctadienyl ethers of glycerol (linear and branched) with a high selectivity into the linear isomer. The corresponding glyceryl monooctyl ethers are obtained by hydrogenation of the octadienyl ethers. The surface properties of these two classes of compounds have been appraised and compared showing the influence of the double bonds on these properties.