AbstractBlending poly(butylene succinate) (PBS) with polylactide (PLLA) has proven effective in improving heat resistance of PLLA fibers. Unfortunately, it remains challenging to maintain good spinnability for PLLA/PBS blends with high content of PBS with which further improved heat resistance could be anticipated. In this study, reactive melt‐extrusion was devised to in‐situ generate PLLA‐PBS copolymers by introducing zinc acetate as a transesterification catalyst into PLLA/PBS blends. The compatibility between the PLLA and PBS phases was greatly improved by the formation of PLLA‐PBS copolymers, resulting in excellent melt‐spinnability even for the PLLA/PBS blends with high PBS content up to 20 wt%. In addition, an increase in crystallinity of PLLA was achieved in PLLA/PBS blend fibers, thanks to the enhanced compatibility. More importantly, the presence of PBS nuclei retarded the molecular orientation of the amorphous PLLA phase, consistent with the effective results from the relaxation heat‐setting treatment. These led to an exceptionally improved heat resistance of the PLLA/PBS blend fibers. As an encouraging result, the boiling water shrinkage was significantly reduced from ca. 20% for neat PLLA fibers to 3.7% for the PLLA/PBS blend fibers with 20 wt% PBS content. These findings may open up a facile and effective route to develop PLLA/PBS blend fibers showing sound spinnability, greatly improved heat resistance and softness.