N-(3,5-Bis(trifluoromethyl)phenyl)-1H-indole-2-carboxamide 1e is an efficient hydrogen-bonding organocatalyst for the ring-opening polymerization of l-lactide. This new catalytic species does control the dispersity (1.08) and molecular weight (3460 g/mol vs 3064 in theory) of the poly(l-lactides) prepared in 2 h. (1)H NMR analysis showed that compound 1e complexes l-lactide in CDCl(3) through the two available NH groups (amide and indole). In particular, the catalytic species appeared to be mainly the H-bonding donor amide (1e in extended conformation, alone or dimer (1e)(2)) and, to a lesser extend, the dual H-bonding amido-indole (1e in its the pinched conformation). The first X-ray structure of the complex between a H-bonding organocatalyst and l-lactide also revealed a tight H-bonded network between the dimer (1e)(2) and l-lactide.