In current power station boilers, fuel burns at a low temperature, which results in low exergy efficiency. This research combined the second law of t with the boiler structure to maximize the efficiency of a 350 MW power plant boiler. A three-dimensional simulation of the combustion process at the power plant boiler is performed. A one-dimensional simulation model of the boiler is then constructed to calculate the combustion exergy loss, heat transfer exergy loss, and boiler exergy efficiency. Under the principle of high-temperature air combustion technologies, this paper also proposes a new structure and improved operating parameters to improve the exergy efficiency of boilers by reducing the heat exchange area of the economizer and increasing the heat exchange area of the air preheater. Simulation results show that the exergy efficiency of the boiler increased from 47.29% to 48.35% through the modified model. The simulation outcomes can instruct future optimal boiler design and controls.