The mechanisms of hydronium- and hydroxide-catalyzed formaldehyde hydrations were investigated by quantum mechanical/molecular mechanical molecular dynamics in combination with flexible coordinates. A stepwise bimolecular and a concerted termolecular mechanism were found with a hydronium catalyst. The latter is more favorable and better consistent with experiment. Structurally, a dipole-bound species initially arranges the nucleophile in a favorable configuration for both routes, significantly enhancing the reactive collisions. On the one hand, the hydronium catalyst also plays a role of a reactant in the bimolecular path. On the other hand, only a stepwise mechanism was found with a hydroxide catalyst. Overall, hydroxide is a stronger catalyst than a hydronium when it is in contact distance with formaldehyde.