Poly(lactic- co -glycolic acid) (PLGA) is among the most common of biodegradable polymers studied in various biomedical applications such as drug delivery and tissue engineering. To facilitate the understanding of the often overlooked PLGA microstructure on important factors affecting PLGA performance, we measured four key parameters of 17 commonly used commercial PLGA polymers (Resomer ®, Expansorb ®, Purasorb ®, Lactel ®, and Wako ® ) by NMR spectroscopy. 1 HNMR and 13 CNMR spectra were used to determine lactic to glycolic ratio (L/G ratio), polymer end-capping, glycolic blockiness ( Rc ), and average glycolic and lactic block lengths ( L G and L L ). In PLGAs with a labeled L/G ratio of 50/50 and acid end capping, the actual lactic content slightly decreased as molecular weight increased in both Resomer ® and Expansorb ®. Whether or not acid- or ester-, termination of these PLGAs was confirmed to be consistent with their brand labels. Moreover, in the ester end-capped 75/25 L/G ratio group, the blockiness value ( Rc ) of Resomer ® RG 756S ( Rc : 1.7) was highest in its group; whereas for the 50/50 acid end-capped group, Expansorb ® DLG 50-2A ( Rc : 1.9) displayed notably higher values than their counterparts. Resomer ® RG 502 ( L L : 2.6, L G : 2.5) and Expansorb ® DLG 50-2E ( L L : 2.5, L G : 2.6) showed the lowest block lengths, suggesting they may undergo a steadier hydrolytic process compared to random, heterogeneously distributed PLGA.