This study examines the effects of manganese oxide octahedral molecular sieve chitosan microspheres (Fe3O4@OMS-2@CTS) on anaerobic and aerobic microbial communities during sewage biological treatment. The addition of Fe3O4@OMS-2@CTS (0.25 g/L) resulted in enhanced levels of operational performance for decolourization dye X-3B. However, degradation dye X-3B inhibition in the presence of Fe3O4@OMS-2@CTS was recorded as greater than or equal to 1.00 g/L. Illumina MiSeq high throughput sequencing of the 16 S rRNA gene showed that 108 genera were observed during the anaerobic process, while only 71 genera were observed during the aerobic process. The largest genera (Aequorivita) decreased from 21.14% to 12.65% and the Pseudomonas genera increased from 10.57% to 12.96% according to the abundance in the presence of 0.25 g/L Fe3O4@OMS-2@CTS during the anaerobic process. The largest Gemmatimonas genera decreased from 21.46% to 11.68% and the Isosphaerae genera increased from 5.8% to 11.98% according to the abundance in the presence of 0.25 g/L Fe3O4@OMS-2@CTS during the aerobic process. Moreover, the X-ray photoelectron spectroscopy results show that the valence states of Mn and Fe in Fe3O4@OMS-2@CTS changed during sewage biological treatment.