Polylactic acid (PLA) is a biodegradable thermoplastic polyester produced from natural resources. Because of its brittleness, many tougheners have been developed. However, traditional toughening methods cause either the loss of modulus and strength or the lack of degradability. In this work, we synthesized a biobased and potentially biodegradable poly(butylene 2,5-furandicarboxylate)-b-poly(ethylene glycol) (PBFEG50) copolymer to toughen PLA, with the purpose of both keeping mechanical strength and enhancing the toughness. The blend containing 5 wt % PBFEG50 exhibited about 28.5 times increase in elongation at break (5.5% vs 156.5%). At the same time, the tensile modulus even strikingly increased by 21.6% while the tensile strength was seldom deteriorated. Such a phenomenon could be explained by the stretch-induced crystallization of the BF segment and the interconnected morphology of PBFEG50 domains in PLA5. The Raman spectrum was used to identify the phase dispersion of PLA and PBFEG50 phases. As the PBFEG50 content increased, the interconnected PBFEG50 domains start to separate, but their size increases. Interestingly, tensile-induced cavitation could be clearly identified in scanning electron microscopy images, which meant that the miscibility between PLA and PBFEG50 was limited. The crystallization of PLA/PBFEG50 blends was examined by differential scanning calorimetry, and the plasticizer effect of the EG segment on the PLA matrix could be confirmed. The rheological experiment revealed decreased viscosity of PLA/PBFEG50 blends, implying the possible greener processing. Finally, potential biodegradability of these blends was proved.