Herein, we evaluated the hydrophilic or hydrophobic surface properties of various oxides using vibrational spectroscopy, such as FT-IR (mid-IR) and near-IR spectroscopy. Pristine SiO 2 showed hydrophobic properties because H 2 O molecules weakly interacted with the hydroxyl groups via hydrogen bonding. Furthermore, the hydrophobic SiO 2 adsorbed less toluene, as a hydrophobic probe molecule. In case of the alkyl-groups-modified SiO 2 , H 2 O molecules were barely adsorbed on the surface even in air, confirming the water-repellent property. The TiO 2 and Al 2 O 3 surfaces adsorbed larger amounts of H 2 O than did pristine SiO 2 , indicating hydrophilic properties, because the Ti 4+ and Al 3+ sites play an essential role in strong interactions with H 2 O molecules via coordinative adsorption. Furthermore, the hydrophilic TiO 2 and Al 2 O 3 showed a high affinity to toluene, indicating oleophilic (affinity to oil or non-polar compounds) properties, because the aromatic compounds were adsorbed on the cation sites by cation-π interaction. Moreover, MgO reacted with H 2 O molecules to yield Mg(OH) 2 , indicating a greater hydrophilicity than TiO 2 or Al 2 O 3 . Based on the considerations, when evaluating the hydrophilic or hydrophobic properties of oxide surfaces, the hydroxyl groups and the cation sites on the surface must be considered.