Biodegradable poly(lactide acid) (PLA) has been well-studied as a shape memory polymer in recent years, but the brittleness and relatively high Tg limit its applications. In this study, a series of PLA/poly(ethylene glycol) (PEG) blends were manufactured by using the solvent evaporation method. The thermal behaviors, morphology, hydrophilicity, and mechanical properties of the samples with different contents of PEG have been experimentally studied by differential scanning calorimetry, scanning electronic microscopy, water contact angle, dynamic mechanical analysis, and tensile test. Furthermore, the influence of PEG on the shape memory properties under different loading conditions including the stretch strain, recovery temperature, deformation temperature, and tensile rate were explored systematically. Experimental results reveal that introduction of appropriate contents of the plasticizer PEG into the PLA/PEG systems results in the significant improvement of morphology, hydrophilicity, and mechanical properties while the high shape memory properties are still retained.