Interactions between coal matrix and organics are vital for adsorption [1], surfactant adsorption on lignite [2-5], and solid–liquid separation of coal slurry [6-10]. Herein, for studying the interaction between hydrophobic surface (coal surface) and small molecules (organics), we measured interactions between organics [nitro and phenyl, pyridine, phenyl, alkyl chain (hexyl) or cycloalkyl (hexyl)] and the coal matrix (liptinite or inertinite) using atomic force microscopy. The strength of interaction followed the order: nitro and phenyl > pyridine > phenyl > alkyl chain (hexyl) > cycloalkyl (hexyl), and liptinite > inertinite. The liptinite has a greater hydrophobicity than inertinite, the greater the attraction force. The lignite surface and coal slurry were modified in an aqueous solution using five surfactants (dodecyl trimethyl ammonium chloride, DTAC; hexadecyl trimethyl ammonium chloride, CTAC; octadecyl trimethyl ammonium chloride, STAC; hexadecyl dimethyl benzyl ammonium chloride, HDBAC; and cetyl pyridine chloride, CPC). Subsequently, the moisture adsorption on treated lignite coal surface and the sedimentation of the treated tails was compared to characterize hydrophobic modifications which showed the order of CTAC > HDBAC > DTAC > CPC > STAC. Thus, the interaction between coal surface and organics needs to consider two rules: 1) The desolvation or the hydrophobic property of the coal surface; 2) The VDW force of the organics. The nature of the difference between rules No. 1 and 2 is that with the size of hydrophobic molecules increased to a surface, the H-bond structure between water molecules in the around would change a lot, which formats great hydrophobic property or desolvation. SynopsisInteraction between organic reagents and coal reveals the mechanism of restraining moisture reabsorption of lignite and solid–liquid separation of coal slurry by organics.