The resonance Raman spectra of palladium(II)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol chloride complex (PdLCl) adsorbed at liquid-liquid interfaces were studied by a centrifugal liquid membrane-resonance Raman microprobe spectroscopy (CLM-RRMS). CLM-RRMS measures the individual resonance Raman spectra of PdLCl at the interface and in the bulk phases. The Raman shifts of PdLCl adsorbed at the heptane/water and toluene/water interfaces were not in agreement with those in toluene and chloroform of lower dielectric constants, but close to those in aqueous alcohol mixed solvents of higher dielectric constants. The intensity ratios of the azo and imine bands decreased with the increase in the dielectric constants of solvents. Solvent effect on the electronic spectra of PdLCl also supported this relationship. The azo-imine intensity ratio in the interfacial Raman spectra suggested that the ligand of PdLCl at the toluene/water and heptane/water interfaces exists under the strong influence of aqueous phase with the dielectric constants of 62 and 40 for the interface, respectively. The present study demonstrated that CLM-RRMS was a powerful technique for the examination of a resonance state of the interfacial pyridylazo-complex, and that the dielectric property of the liquid-liquid interface could be probed from the measurement of the azo-imine equilibria.