Tuning the Printing Stability and Hydrolytic Degradation of Melt‐Electrowritten Poly(lactic‐co‐glycolic acid) Scaffolds Through Copolymer Composition

Poly(lactic‐co‐glycolic acid) (PLGA) is a promising biodegradable polymer for melt electrowriting (MEW), yet how composition governs processing stability and degradation remains unclear. Here, ordered microfibrous scaffolds were fabricated by MEW using PLGA with lactic acid‐to‐glycolic acid (LA‐to‐GA) ratios of 80:20, 70:30, and 50:50. Processing stability was evaluated via continuous printing, followed by 6‐month in vitro hydrolytic degradation. Morphology, thermal transitions, molecular weight, weight loss, and mechanics were characterized. All compositions showed progressive jet‐speed increases and gradual mechanical deterioration during prolonged MEW, indicating thermally induced changes in melt processability. During degradation, higher GA content accelerated molecular‐weight reduction, weight loss, and structural collapse. After 8 weeks, PLGA (80:20), PLGA (70:30), and PLGA (50:50) exhibited approximately 36%, 68%, and 90% weight loss, respectively. Molecular weight declined substantially before measurable weight loss in all formulations, consistent with bulk degradation. Hydrolysis‐induced molecular rearrangement and crystallization occurred in PLGA (80:20) and PLGA (70:30), whereas amorphous PLGA (50:50) underwent rapid structural failure without comparable thermal transitions. These results demonstrate that the LA‐to‐GA ratio governs degradation kinetics, long‐term processing stability, and mechanical durability of MEW‐fabricated PLGA scaffolds. This work provides guidelines for designing biodegradable scaffolds with tunable degradation for tissue engineering and biomedical applications.