The conformation of tert-butyloxycarbonyl-Tyr-Gly-Gly-(4-bromo)Phe-Met-OH, as a monoanionic derivative of Met-enkephalin, was elucidated by X-ray crystal analysis. The molecule took an extended conformation which was bended at the Phe residue. The implication of the dimer formation caused by 4 intermolecular hydrogen bonds was discussed in the relation with the opiate receptor.