Porous scaffolds for tissue engineering applications based on poly(D,L-lactide)/poly(epsilon-caprolactone) compatibilized blends are described. The addition of a third polymer, namely poly( D, L-lactide-co-caprolactone) copolymer, has a profound effect on morphological properties of the blends scaffolds. In fact, the copolymer acts as compatibilizing agent and reduces the dimension of the dispersed phase of an order of magnitude. Such effect is function of the polymer composition. The efficiency of scaffolds obtained with poly( D, L-lactide) based blends containing 30% by weight of poly(epsilon-caprolactone) as dispersed phase toward hepatocytes has been tested by several biological assays and we found that they are able to promote a perfect adhesion, proliferation and growth of cells. Moreover, the addition of the copolymer significantly improves the biomedical performance of the scaffold.