In this study, high-fidelity simulations are conducted on a 35 MW pulverized coal oxy-fuel boiler to investigate NOx formation characteristics under staged oxy-fuel combustion, including both fuel-staged and oxygen-fuel two-way staged modes. Detailed volatile components are considered by using the chemical percolation devolatilization model. A skeletal reaction mechanisms consisting of 35 species developed for fuel-NOx formation under oxy-fuel conditions are employed for the gas phase combustion and NOx modeling. The radiative property models are also optimized for oxy-fuel combustion. The results show that in the fuel-staged mode, a reduction atmosphere is established in the reburning zone to reduce the NOx concentration in the flue gas. A reduction of 5.6% in the average NO concentration at the furnace outlet is observed relative to the baseline oxy-fuel case. Moreover, the application of oxygen-fuel two-way staged combustion leads to a further reduction in NOx formation. The average NO concentration at the furnace outlet is decreased by 17% compared to the baseline oxy-fuel case. Pathway analysis indicates a reduction in the NO formation pathway involving HCN → NCO → NO, while the NO reduction pathway of NO → HCN is enhanced.