Pulverized coal is still found in many practical devices even though it is recognized as “dirty fuel” because of its CO₂ and pollutant emissions. To overcome this problem, advanced coal utilization technologies have been developed using numerical simulations. In this study, the structures of the laminar counter-flow diffusion flames of pulverized coals were investigated by performing simulations based on detailed chemistry. The high-temperature region became narrower as the coal/air ratio increased, because of the departure from the stoichiometric mixture and local quenching by the heat transfer between the gas and solid phases. Further, the applicability of the flamelet/progress-variable (FPV) model was investigated through a priori and a posteriori tests. The a priori test confirmed that the FPV model is capable of reproducing the numerical solutions obtained using the detailed chemistry, including the mass fractions of minor species. In the a posteriori test, there was a slight difference between the FPV model and detailed chemistry results due to overestimation of the progress of the chemical reactions. Given the sufficiently high accuracy of the FPV model in various numerical conditions, it can be concluded that the extended FPV model has potential for use in turbulent coal combustion simulations.