Electronic structure calculations of the pertinent stationary points on the potential energy surface show that carboxylic acids can act effectively as catalysts in the hydration of acetaldehyde. Barriers to this catalyzed process correlate strongly with the pK(a) of the acid, providing the potential to provide the predictive capacity of the effectiveness of carboxylic acid catalysts. Transition states for the acid-catalyzed systems take the form of pseudo-six-membered rings through the linear nature of their hydrogen bonds, which accounts for their relative stability compared to the more strained direct and water-catalyzed systems. When considered as a stepwise reaction of a dimerization followed by reaction/complexation, it is likely that collisional stabilization of the prereactive complex is more likely than reaction in the free gas phase, although the catalyzed hydration does retain the potential to proceed on water surfaces or in droplets. Lastly, it is observed that postreactive diol-acid complexes are significantly stable (similar to 12-17 kcal/mol) relative to isolated products, suggesting the possibility of long-lived hygroscopic species that could act as a seed molecule for condensation of secondary organic aerosols.