When treating municipal wastewater, nitrogen removal is often limited due to low C/N, which needs to be compensated for by additional carbon source injections. This study investigated the feasibility of using industrial-waste polyglycolic acid (PGA) as a carbon source for denitrification in an SBR to obtain an economical carbon source. The results revealed that an optimal denitrification performance in a methanol-fed activated sludge system was achieved with a PGA dosage of 1.2 mL/L, a pH of 7–8, and a dissolved-oxygen (DO) concentration of 3 ± 0.5 mg/L. Under these conditions, all quality parameters for effluent water met the required criteria [COD < 50 mg/L; TN < 15 mg/L; NH4+-N < 5(8) mg/L]. PGA enhanced the variety and richness of microbial communities, thereby markedly increasing the relative abundance of major phyla such as Proteobacteria and Bacteroidota and major genera such as Paracoccus and Dechloromonas. Furthermore, PGA upregulated the expression of nitrogen-metabolism-related genera, including amo, hao, nar, and nor, which improved the denitrification performance of the system. This study provides a reference for applying PGA as a carbon source for low-C/N-wastewater treatment and solid-waste utilization.