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The issue of coal spontaneous combustion greatly threatens the production safety of coal mining, storage, and transportation. It is significant to study oxygen adsorption to understand the mechanism of coal spontaneous combustion. In this paper, based on the fractal dimension of coal and the self-similar fractal geometry, the internal pore structure of coal is modeled. Then, the lattice Boltzmann method is employed to conduct the numerical simulation of oxygen adsorption in coal. Compared with the existing experimental data and numerical simulation, the lattice Boltzmann method is verified to be correct. The numerical results indicate that in the process of oxygen adsorption in coal, the preferential flow occurs when the large pores connect to the channel. In the meantime, the large diffusion coefficient leads to an early time for adsorption equilibrium. The oxygen adsorption increases with an increased adsorption rate constant. Pore structure plays a significant role in the adsorption behavior of oxygen in coal. The results can provide theoretical support for reducing coal spontaneous combustion and ensuring coal mine safety in production.