Hydrated clusters of 2-phenylethyl alcohol (PEAL) and 2-phenylethlyamine (PEA have been studied in a jet-cooled environment, using laser-induced fluorescence excitation and mass-selected resonant two-photon ionization (R2PI) spectroscopy of the S-1<--S-0 electronic transitions. Spectral features have been observed for clusters M(H2O)(n) n=1-4, and their stoichiometry assigned on the basis of the ion fragmentation patterns. Ionization of hydrated PEA(H2O)(n) clusters leads to the observation of PEA(H2O)(n-1)(+) and CH2NH2(H2O)(n)(+) ions. Partially resolved rotational band contours of several n=1,2 clusters have been analyzed with the aid of ab initio molecular orbital calculations, conducted at the MP2/6-31G*/HF/6-31G* level for the ground state, and CIS/6-31G* for the first electronically excited singlet state. The analysis reveals the supramolecular structure: the host molecular conformation within these clusters and the binding sites of the water molecules. In n=1 clusters of 2-phenylethylamine, the primary binding site involves hydrogen bonding to the nitrogen atom in the amine group. Cyclic hydrogen-bonded structures are observed for n=2 clusters. In 2-phenylethyl alcohol, two different 1:1 clusters have been assigned in which the water molecule binds alternatively as a proton acceptor and proton donor. Further interactions between water molecules and the host , e.g. H-water...pi and O-water...HC, lead to additional stabilization of certain complexes. The assignments are aided greatly by the extraordinary sensitivity of the S-1<--S-0 transition moment alignment to both side chain conformation and long-range intermolecular interactions.