We report experimental realization of Raman spectra enhancement of copper phthalocyanine, using an on-chip metallic planar waveguide of the sub-millimeter scale. The oscillating ultrahigh order modes excited by the direct coupling method yield high optical intensity at resonance, which is different from the conventional strategy to create localized “hot spots.” The observed excitation efficiency of the Raman signal is significantly enhanced, owing to the high Q factor of the resonant cavity. Furthermore, effective modulation of the Raman intensity is available by adjusting the polymethyl methacrylate (PMMA) thickness in the guiding layer, i.e., by tuning the light–matter interaction length. A large modulation depth is verified through the fact that 10 times variation in the enhancement factor is observed in the experiment as the PMMA thickness varies from 7 to 23 μm.