A synthetic protocol for the preparation of α-acyl aminocarboxamides and α-amino amidines is proposed. The selectivity toward each of these two possible products was tuned by simple modifications of the reaction conditions. A broad scope is presented, allowing access to the desired products in up to 87% (Ugi adduct) and 93% (α-amino amidine). Theoretical calculations were carried out, and the analysis led to the proposal of a new mechanistic pathway for the Ugi reaction, in which methanol acts not only as the solvent but also as a reagent. High-resolution (tandem) mass spectrometry experiments allowed the detection and characterization of the key intermediate associated with this new and alternative reaction pathway, thus supporting the theoretical proposal.