The structure of the phenylacetylene-water complex has been elucidated based on spectral shifts in electronic and vibrational transitions. Phenylacetylene forms a cyclic complex with water incorporating C-H center dot center dot center dot O and O-H center dot center dot center dot pi hydrogen bonds, which is different from both the benzene-water and acetylene-water complexes, even though phenylacetylene combines the features of both benzene and acetylene. Formation of such a complex can be rationalized on the basis of cooperativity between the two sets of hydrogen bonds.