An oxygen-rich and low NOx burner integrated with liquefied natural gas (LNG) was proposed to address unstable combustion and high NOx emissions from a 330 MW subcritical boiler under ultra-low load operation in China. To assess the effectiveness of the retrofit, Chemkin and Fluent softwares were utilized to construct a new NOx model and calculate NOx generation, based on the combustion of pulverized coal gas and LNG. Further, an eddy dissipation concept (EDC) model, which can reflect detailed chemical reactions, was applied to calculate gas-phase reactions in the furnace. The results showed that when performing the deep peak shaving after the retrofit, the combustion in the furnace was stable under 50% or more load, and NOx emission level at the furnace outlet was lower than 350 mg/m3 (6% O2 content, dry basis). Under 25% load, the oxygen-rich burner integrated with LNG was applied, and the pulverized coal flow entered the furnace in a state of high-intensity combustion, which effectively promoted the stability of combustion in the furnace. The reductive combustion state with reductive free radicals generated by LNG decomposition inhibited NOx formation. Consequently, NOx emissions from the furnace outlet decreased from 380 mg/m3 to 316 mg/m3.