The design of industrial products based on bioresources is a challenging issue. Modification of starch, by hydrophobic chemical substituents, results in an innovative hydrophobic material. Herein, the hydrophobic part of the derivative, comprised of octadienyl chains, is introduced through catalytic butadiene telomerization. The process is efficiently conducted on starch in its granular form in an aqueous medium using hydrosoluble palladium complexes. After optimization, a turnover number (TON) of up to 550 was achieved in the presence of [(π-allyl)PdCl]2 catalyst and, unusually, by using dimethylisosorbide as a cosolvent.