We studied the orientation of inhomogeneous media 5CB absorbed on nano-roughened Ag and Au Electrodes by using Surface-Enhanced Raman Scattering. Our results first suggest that the orientation of 5CB absorbed on nano-roughened Ag electrode is different from that of Au electrode. This implies that the interaction between inhomogeneous media 5CB and Ag is different from the interaction between inhomogeneous media 5CB and Au. The conclusion is that the orientation of 5CB absorbed on nano-roughened Ag electrode is perpendicular, and the orientation of 5CB absorbed on nano-roughened Au electrode is more complicated, including parallel, perpendicular and tilted.