Telomerization of butadiene into octadienols in a micellar system and in the presence of hydrophilic or hydrophobic phosphines derived from triphenylphosphine has been investigated. Activities and selectivities were strongly dependent on the steric properties of the phosphine and on the nature of the surfactant/phosphine couple. The best results have been obtained with the water-soluble phosphine/cationic surfactant combinations (octadienols selectivities > 70% and turnover frequencies up to 830 h(-1)). The phosphine/anionic surfactant couples gave rise to octadienols in poor selectivities (40%) and activities (100 h(-1)). With the phosphine/neutral surfactant combinations, the results are strongly dependent on the nature of the phosphine. These results are interpreted from electrostatic interactions at the micelle-water interfaces.