Both AB diblock and ABA triblock copolymers consisting of poly(l-lactide) (PLLA: A) and poly(ethylene glycol) (PEG: B) were deposited on a silicon surface on which poly(d-lactide) (PDLA) had been preimmobilized. The deposit of the diblock copolymer (PLLA-PEG) formed band structures similar to those observed when the same copolymer was directly deposited on the silicon surface. In contrast, the deposit of the triblock copolymer (PLLA-PEG-PLLA) formed many particulates scattering over the surface. When the PLLA-PEG deposit was subjected to water-soaking, the original band morphology was completely replaced by the particulate morphology that was identical to that of the PLLA-PEG-PLLA deposit. Their FT-IR analyses revealed that both copolymers had been bound through the stereocomplex (sc) formation between the preimmobilized PDLA chains and the PLLA blocks of the copolymers. Grazing-incidence small-angle X-ray scattering (GISAXS) also supported these surface morphologies. It was therefore evident that hydrophilic PEG chains can be immobilized on the PDLA-preimmobilized surface by the sc formation.