In this study, the effects of elevated COD/N ratios on nitrogen removal, production and composition of the extracellular polymer substances (EPSs) and microbial community of a completely autotrophic nitrogen removal via nitrite (CANON) process were studied in a sequencing batch membrane bioreactor (SBMBR). The whole experiment was divided into two stages: the CANON stage (without organic matter in influent) and the simultaneous partial nitrification, anaerobic ammonia oxidation and denitrification (SNAD) stage (with organic matter in influent). When the inflow ammonia nitrogen was 420 mg/L and the COD/N ratio was no higher than 0.8, the addition of COD was helpful to the CANON process; the total nitrogen removal efficiency (TNE) was improved from approximately 65% to more than 75%, and the nitrogen removal rate (NRR) was improved from approximately 0.255 kgN/(m3·d) to approximately 0.278 kgN/(m3•d), while the TNE decreased to 60%, and the NRR decreased to 0.236 kgN/(m3•d) when the COD/N ratio was elevated to 1.0. For the EPSs, the amounts of soluble EPS (SEPS) and loosely bound EPS (LB-EPS) were both higher in the CANON stage than in the SNAD stage, while the amount of tightly bound EPS (TB-EPS) in the SNAD stage was significantly higher due to the proliferation of heterotrophic bacteria. The metagenome sequencing technique was used to analyse the microbial community in the SBMBR. The results showed that the addition of COD altered the structure of the bacterial community in the SBMBR. The amounts of Candidatus Anammoxoglobus of anaerobic ammonia oxidation bacteria (AAOB) and Nitrosomonas of ammonia oxidizing bacteria (AOB) both decreased significantly, and Nitrospira of nitrite oxidizing bacteria (NOB) was always in the reactor, although the amount changed slightly. A proliferation of denitrifiers related to the genera of Thauera, Dokdonella and Azospira was found in the SBMBR.