The use of a custom-made palladium complex for the telomerisation of isoprene with alcohols under green conditions is described. Using a very low catalyst loading (0.1 mol%), this protocol allows for the reactions to be carried out without the need of high pressure equipment, at room temperature and under solventless conditions, affording high yields of telomerization products with high selectivity towards linear head-to-head and tail-to-head telomers.