Raman spectra of ring-breathing (ν₁₂) and CN stretching vibrations (ν_CN) of jet-cooled benzonitrile and its clusters with Ar, H₂O, CH₃OH, CH₃CN, CCl₄, CHCl₃ and CHF₃ were observed by stimulated Raman-UV double resonance spectroscopy. Cluster structures were determined on the basis of the observed vibrational spectra, rotational contour analyses of the high resolution S₁-S₀ electronic spectra and ab initio molecular orbital calculations with the HF/6-31G(d,p) basis set. It was found that the types of the cluster structures are classified into three groups. (1) The clusters with H₂O, CH₃OH and CH₃CN represent the ‘side’-type structure, in which the intermolecular bond is formed in the phynyl plane of benzonitrile, and the benzonitrile dimer also belongs to this structure. (2) The clusters with Ar and CCl₄ form the ‘on-top’-type strucure, where Ar or CCl₄ is located above the phenyl plane. (3) The clusters with CHCl₃ and CHF₃ have ‘linear’-type structure, in which these molecules are located at the N end of the CN group of benzonitrile. The rate constants of the vibrational relaxation for these clusters occurring after the Raman excitation to their ν₁₂ vibrations were also observed. It was found that different rate constants are associated with the different types of cluster structures. That is, the 12₁ levels of the ‘side’-type clusters relax much faster than those of other types of the clusters. The results represent a clear indication that the anharmonic couping between ν₁₂ and intermolecular vibrations are much larger in the ‘side’-type clusters than others.