A new method of resonance Raman microprobe spectroscopy combined with a centrifugal liquid membrane (CLM) method was constructed and successfully applied to the detection of the complex of palladium(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) formed at the heptane/water interface. The depth profiles of resonance Raman intensities of Pd(II)-5-Br-PADAP complex along the axis perpendicular to the interface confirmed that the complex existed only at the liquid-liquid interface.