We observed several intermolecular complexes involving H₂O or H₂S with benzyl alcohol and benzyl mercaptan, analysing the microsolvation and hydrogen bonding competition between the two hydrides. The clusters were generated in a jet-cooled expansion and characterized using chirped-pulse Fourier-transform microwave spectroscopy in the region 2-8 GHz. In the benzyl alcohol monosolvates, the aromatic alcohol acts as a proton donor, in opposition to the benzyl mercaptan dimers where the thiol group acts as a proton acceptor. For the bisolvated trimers, we observed two H₂O or H₂S molecules binding to benzyl alcohol and two water molecules attaching to benzyl mercaptan, always stabilized by cooperative hydrogen bonding. The clusters additionally involved secondary interactions between the solvents and the π ring system. Detailed information on the noncovalent interactions and molecular structures results from the combination of rotational data and DFT and ab initio molecular orbital calculations.