The stereocomplex formation of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA) using an inkjet system was expanded to the amphiphilic copolymers, using poly(ethylene glycol) (PEG) as a hydrophilic polymer. The diblock copolymers, which are composed of PEG and PLLA (MPEG-co-PLLA) and PEG and PDLA (MPEG-co-PDLA), were employed for thin-film preparation using an aqueous inkjet system. The solvent and temperature conditions were optimized for the stereocomplex formation between MPEG-co-PLLA and MPEG-co- PDLA. As a result, the stereocomplex was adequately formed in acetonitrile/water (1:1, v/v) at 40 °C. The aqueous conditions improved the stereocomplex film preparation, which have suffered from clogging when using the organic solvents in previous work. The triblock copolymers, PLLA-co-PEG-co-PLLA and PDLA-co-PEG-co-PDLA, were employed for square patterning with the inkjet system, which produced thin films. The amphiphilic polymer film was able to retain hydrophobic compounds inside. The present result contributed to the rapid film preparation by inkjet, retaining drugs with difficult solubility in water, such as paclitaxel within the films.