The liquid-vapor interface is playing an important role in aerosol and cloud chemistry in cloud droplet activation by aerosol particles and potentially also in ice nucleation. We have employed the surface sensitive and chemically selective X-ray photoelectron spectroscopy (XPS) technique to examine the liquid-vapor interface for mixtures of water and small alcohols or small carboxylic acids (C1 to C4), abundant chemicals in the atmosphere in concentration ranges relevant for cloud chemistry or aerosol particles at the point of activation into a cloud droplet. A linear correlation was found between the headgroup carbon 1s core-level signal intensity and the surface excess derived from literature surface tension data with the offset being explained by the bulk contribution to the photoemission signal. The relative interfacial enhancement of the carboxylic acids over the carboxylates at the same bulk concentration was found to be highest (nearly 20) for propionic acid/propionate and still about 5 for formic acid/formate, also in fair agreement with surface tension measurements. This provides direct spectroscopic evidence for high carboxylic acid concentrations at aqueous solution-air interfaces that may be responsible for acid catalyzed chemistry under moderately acidic conditions with respect to their bulk aqueous phase acidity constant. By assessing the ratio of aliphatic to headgroup C 1s signal intensities XPS also provides information about the orientation of the molecules. The results indicate an increasing orientation of alcohols and neutral acids toward the surface normal as a function of chain length, along with increasing importance of lateral hydrophobic interactions at higher surface coverage. In turn, the carboxylate ions exhibit stronger orientation toward the surface normal than the corresponding neutral acids, likely caused by the stronger hydration of the charged headgroup.