The whole controlled synthesis of novel amphiphilic polylactide (PLA)grafted dextran copolymers was achieved. The control of the architecture of such biodegradable and potentially biocompatible copolymers has required a three-step synthesis based on the "grafting from" concept. The first step consisted of the partial silylation of the dextran hydroxyl groups. This protection step was followed by the ring-opening polymerization of D,L-lactide initiated from the remaining OH functions of the partially silylated polysaccharide. The third step involved the silylether group deprotection under very mild conditions. Based on previous studies, in which the control of the first step was achieved, this study is focused on the last two steps. Experimental conditions were investigated to ensure a controlled polymerization of D,L-lactide, in terms of grafting efficiency, graft length, and transesterifi cation limitation. After polymerization, the final step was studied in order to avoid degradation of both polysaccharide backbone and polyester grafts. The chemical stability of dextran backbone was checked throughout each step of the synthesis. PLA-grafted dextrans and PLA-grafted (silylated dextrans) were proved to adopt a core-shell conformation in Various solvents. Furthermore, preliminary experiments on the potential use of these amphiphilic grafted copolymers as liquid/liquid interface stabilizers were performed. (C) 2004 Wiley Periodicals, Inc.