A peptide biphenyl hybrid compound {systematic name: dimethyl 2,2′-[((2S,2′S)-2,2′-{[(2S,2′S)-1,1′-([1,1′-biphenyl]-2,2′-dicarbonyl)bis(pyrrolidine-1,2-diyl-2-carbonyl)]bis(azanediyl)}bis(3-phenylpropanoyl))bis(azanediyl)](2S,2′S)-dipropionate hemihydrate}, C50H56N6O10·0.5H2O, was prepared by coupling of [1,1′-biphenyl]-2,2′-dicarbonyl dichloride, triethylamine and the tripeptide Pro–Phe–Ala in CH2Cl2 at 273 K under an N2 atmosphere. In the crystal, the asymmetric unit contains the peptide biphenyl hybrid accompanied by one-half of a water molecule. A C atom of one of the proline rings is disordered between two positions in a 0.746 (11):0.254 (11) ratio. An important structural aspect of peptide compounds is their capacity to self-associate mediated by intermolecular and intramolecular hydrogen bonding. This characteristic can be useful in understanding the interactions between peptides and biomacromolecular targets, as well as to explain peptide properties.