The hydrogen-bonded complexes of phenylacetylene, 4-fluorophenylacetylene, 2-fluorophenylacetylene and 4-cyanophenylacetylene with water were investigated using IR-UV double resonance spectroscopy. Phenylacetylene, 4- fluorophenylacetylene, 2-fluorophenylacetylene and 4-cyanophenylacetylene form quasi-planar cyclic complexes with water incorporating C-H O and O-H p hydrogen bonds. In the case of phenylacetylene, 4-fluorophenylacetylene and 2-fluorophenylacetylene complexes the p electron density of the acetylenic C=C bond acts as an acceptor to the O-H π hydrogen bond, while in the case of 4-cyanophenylacetylene complex it's the p electron density of the C:N bond is the acceptor. A second water complex was also observed for 2- fluorophenylacetylene in which water interacts with fluorine atom and acetylenic C=C bond rendering a double donor motif for the water molecule. One of the most interesting features of water complexes of 4-fluorophenylacetylene and 2-fluorophenylacetylene is the preference of p hydrogen bond over r hydrogen bond. © 2012 IACS.