The interaction between amylopectin, a starch polysaccharide, and ethylene glycol (EG) was investigated using broad-band dielectric relaxation spectroscopy. Water-free amylopectin (AP) was mixed with 21 wt % ethylene glycol. This resulted in a continuous ethylene glycol phase, as well as a molecularly mixed AP/EG fraction. After storage at room temperature or annealing, the mixture shows dynamic properties typical of a polymer with weak intermolecular interactions, suggesting that EG binds preferentially to AP and forms intrachain H-bridges leading to increased chain stiffness and thus an increased glass transition temperature. This structure evolution is accompanied by a sharp reduction in the size of the ethylene glycol droplets to a few nanometers, as revealed by pronounced confinement effects in the alpha -relaxation of the dispersed EG.