Vibrational and electronic spectra of the benzene-benzyl alcohol hetero-dimer ion are measured by photodissociation spectroscopy. The vibrational spectrum shows a prominent band at 3662 +/- 3 cm(-1), which is assigned to the stretching vibration of the OH group free from intermolecular perturbations. The electronic spectrum shows a broad band around 950 nm, which arises from a charge resonance interaction between the aromatic rings. These results suggest that the ion has a sandwich-like structure suitable for the resonance interaction, without the hydrogen bond between the OH group of benzyl alcohol and the pi-electrons of benzene.