N-(3,5-Bis(trifluoromethyl)phenyl)-1H-indole-2-carboxamide le 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. H-1 NMR analysis showed that compound le complexes L-lactide in CDCl3 through the two available NH groups (amide and indole). In particular, the catalytic species appeared to be mainly the H-bonding donor amide (le 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.