Oxygen-enriched waste incineration can improve incineration efficiency and reduce pollutant generation, while greenhouse gases and pollutant emission characteristics of different wastes are still unclear. In this study, pollutant emission characteristics of actual municipal solid waste (MSW) and typical components at different oxygen concentrations and moisture content were investigated to reveal the pollutant generation mechanism. The results illustrated that when oxygen concentrations increased from 21% to 30%, CO, CH4 and HCN emissions decreased by 95%, 95.5% and 96.5%, respectively. NO emissions increased by 75% due to the promotion of oxygen on fuel NO and rapid NO. The slight increase in SO2 (from 25.8% to 26.87%) was due to the promotion of oxygen on organic S and the reaction between SO42− and HCl. The decrease in HCl emissions (from 78.42% to 76.85%) was caused by the increasing deacon reaction. Besides, with increasing moisture content, CO, CH4 and HCN generation decreased first because of the CO oxidation and CH4 reforming reaction, and then increased due to the water–gas reaction between fixed carbon and water. Furthermore, the moisture content contained (66%) would promote NO and HCl generation by 35.7% and 9.1% through fuel N oxidation by OH radicals and hydrolysis of chlorine salt at high temperatures. The increased oxygen concentration would inhibit the moisture influence and improve applicability for different MSW. In addition, 25% oxygen-enriched incineration was selected as the most suitable parameter for improving combustion efficiency and reducing pollutant emissions of MSW with high moisture content.