The rate constants of intracluster vibrational energy redistribution (IVR) of benzonitrile-(CHCl₃)₁ for the 12₁ (1000 cm^-1), 1₁ (760 cm^-1), and 6a₁ (460 cm^-1) levels have been measured by time-resolved stimulated Raman-UV double resonance spectroscopy. It was found that the observed rate constants are independent of the energies but strongly dependent on the vibrational modes. In order to find a relationship between the structure and the IVR rate, structures of benzonitrile-(CHCl₃)_n=1-3 have been determined based on the results of the Raman spectra and the high resolution S₁-S₀ electronic spectra for the size-selected clusters, and ab initio MO calculations. The Raman spectra were observed for both CHCl₃ and benzonitrile sites. It was found that the CH stretching vibration of the CHCl₃ moiety showed a higher frequency shift in the clusters, whose magnitude depends on the binding site to benzonitrile. For the benzonitrile moiety, the Raman spectra of CH stretch (ν₂), CN stretch (ν_CN), ring breathing (ν₁₂ and ν₁), and CCC in-plane bending (ν_6a) vibrations were investigated. From those results, it was concluded that the clusters have the form such that the CH hydrogen of the first CHCl₃ is hydrogen-bonded to the N end of the CN group, while second and third CHCl₃ are hydrogen-bonded to the phenyl ring. The observed mode dependence of the IVR rate constants will be discussed based on the cluster structure and the vibrational motion.