The use of protonated l-prolinethioamide instead of the free base derivative 1 as the organocatalyst for the direct aldol addition has a profound and appreciable effect on both the yield and the stereochemical course of the reaction. 4-Nitrobenzaldehyde (2) reacts with acetone in the presence of the protonated catalyst 1.TFA, affording aldol product 3 with a yield up to 99% and an ee up to 98%. The catalyst loading can be lowered to 2.5 mol %. More than 20 different acids were investigated as an additive, and its role as cocatalyst has been discussed. Furthermore, reactions of l-prolinethioamide salts with acetone have been monitored using ESI-MS and 1H NMR techniques, giving insight into the mechanism of the direct aldol reaction. The presumed formation of the iminium salt 10 has been unambiguously confirmed.