This study investigated the effect of the Joncryl concentration on the properties of polylactide/poly(ε-caprolactone) (PLA/PCL) and PLA/poly(ethylene glycol) (PEG) blends. The addition of Joncryl influenced the properties of both PLA-based blends. In the blend of PLA/PCL blends, the addition of Joncryl reduced the size of PCL droplets, which implies the compatibility of the two phases, while PLA/PEG blends showed a co-continuous type of morphology at 0.1% and 0.3 wt.% of Joncryl loading. The crystallinity of PCL and PEG was studied on both PLA/PCL and PLA/PEG blend systems. In both scenarios, the crystallinity of the blends decreased upon the addition of Joncryl. Thermal stabilities were shown to depend on the addition of Joncryl. The toughness increased when 0.5 wt.% of Joncryl was added to both systems. However, the stiffness of PLA/PCL decreased, while the stiffness of PLA/PEG increased with the increasing concentration of Joncryl. This study provides new insight into the effect of chain extenders on the compatibility of PLA-based blends.