IR-UV ion-dip spectroscopy has been used to study N-phenylformamide and its hydrated clusters in the ground and excited (S-1) electronic states. Their NH stretch bands readily differentiate cis (3441 cm(-1)) and trans (3463 cm(-1)) isomers. Clusters of trarts-N-phenylformlamide with 1 or 2, water molecules show nearly equal preference for binding to the NH and CO sites. A further cluster is assigned in which a chain of four water molecules form an H-bonded bridge between NH and CO. Its vibrational spectrum is characterised by broad, intense and red-shifted bands resulting from strong cooperative effects and distribution of vibrational motion along the II-bonded chain.