Poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB) copolyester is a novel biodegradable polymer synthesized by microorganisms in recent years, however it cannot meet the people's daily production and living requirements owing to its poor strength. Thanks to their remarkable combination of good strength and high modulus, Poly (lactic acid) (PLA) is mixed with P34HB to enhance its strength, and the chain extender ADR-4370F is selected to modify PLA/P34HB blend via in-situ reaction compatibilization. The incorporation of 0.7 phr ADR into the 70/30 wt% PLA/P34HB blend promotes a remarkable increase of 181% in elongation at break compared to PLA/P34HB with 70/30 wt%. Meanwhile, the Izod impact strength, tensile strength and modulus of PLA blend increases by 60%, 20% and 22% compared with 70/30 wt% PLA/P34HB, respectively. Rheological results demonstrate that storage modulus, loss modulus, and complex viscosity enhance evidently with the elevation of ADR dosage, indicating that the improvement of melt strength is beneficial to the processing and forming of the materials. The compatibilization mechanism is investigated by infrared spectroscopy, and the epoxy groups in ADR is the most important factor to improve the compatibility and the mechanical properties of the blends.