Surface-initiated atom transfer radical polymerization (SI-ATRP) is successfully applied to electrospun constructs of poly(L-lactide). ATRP macroinitiators are adsorbed through polyelectrolyte complexation following the introduction of negative charges on the polyester surface through its blending with a six-armed carboxy-terminated oligolactide. SI-ATRP of glycerol monomethacrylate (GMMA) or 2-(N, N-diethylamino)ethyl methacrylate (DEAEMA) allows then to grow surface films with controllable thickness, and in this way also to control the wetting and interactions of the construct.