By using surface-enhanced Raman scattering (SERS), the orientation of liquid crystal 5CB absorbed on nano-roughened Ag and Au electrodes was studied. The results suggest that the orientation of LC 5CB absorbed on nano-roughened Ag electrode is different from that of Au electrode. This implies that the interaction between LC 5CB and Ag is different from the interaction between LC 5CB and Au. The conclusion is that the orientation of LC 5CB absorbed on nano-roughened Ag electrode is perpendicular, and the oriental ton of LC 5CB absorbed on nano-roughened Au electrode is more complicated, including parallel, perpendicular and tilted.