The catalytic efficiency in organic synthesis of the aqueous extract of the pericarp of Sapindus trifoliatus fruits was evaluated. The synthesis of a series of aldimines from aromatic aldehydes and amines was successfully catalyzed by the extract, whereas aromatic ketones and amines did not yield ketimines under comparable reaction conditions, indicating the chemoselective catalysis of the extract. The catalytic activity of the extract is due to saponins, which have a common structural skeleton containing a pentacyclic triterpenoid part substituted with different carbohydrate side chains. The mild conditions, high yields, and short reaction times not only make this protocol a valuable alternative to the conventional methods, but it also becomes significant under the roof of environmentally greener and safer processes.