A density function approach has been used to screen an appropriate surface modifier for oxidized coal to enhance its hydrophobicity in a flotation process. Two oxidized coal surface models, coal-COOH and coal-COONa, based on the substitution of 10-fused benzene rings with COOH and COONa functional groups, have been constructed to mimic the surface hydrophilic sites at acidic and alkaline pHs, respectively. A nonpolar molecule and five polar candidate molecules with different functional groups have been examined on each oxidized coal model surface. Our present study indicates that octane is ineffective toward increasing the surface hydrophobicity for both coal-COOH and coal-COONa models due to its preferential adsorption on hydrophobic aromatic sheet, although it can spontaneously bind to the coal model surfaces at 298 K. Unlike octane, 4-pentylpyridine will present the preferred hydrophobic conformation on both models. However, its adsorption process is favorable energetically only on the coal-COOH model. The optimized geometries of all four oxygen-containing molecules (1-methoxyheptane, 1-octanol, octanal, and octanoic acid) show that directional hydrogen bonds will be formed between their oxygenated groups and the COOH group of coal-COOH model. This results in the protrusion of the hydrocarbon chain toward the water phase, which is beneficial for increasing coal surface hydrophobicity. However, the calculated Gibbs free energies suggest that octanoic acid is the best candidate. The adsorption of all four oxygen-containing molecules on the coal-COONa model is a spontaneous process. However, only sodium octanoate can be regarded as the effective surface modifier according to its optimized adsorption conformation at alkaline pH.