Casein (and its sodium salt, sodium caseinate, SC) is an inexpensive natural milk protein that is used as a biodegradable biomaterial, especially to produce packaging films. However, to enhance some of its properties, it needs to be blended with other polymers, which should preferably be biodegradable such as poly lactic acid (PLA) and poly ε-caprolactone (PCL). New SC-g-PLA and SC-g-PCL graft copolymers have been prepared and unambiguously characterized, in particular by 1 H and DOSY NMR. The grafting degrees are high (between 24 and 35% by weight) and result in variations of properties, such as hy-drophobicity and thermal properties. The microstructures of SC/PLA and SC/PCL blends were studied and compared, with and without the addition of the SC-g-PLA and SC-g-PCL copolymers to test the com-patibilization capacity of these new biodegradable copolymers.