Based on a highly sensitive new generation confocal microprobe Raman system, the adsorption behavior of thiocyanate (SCN-) on a gold electrode in methanol solution was investigated by SERS for the first time. Preliminary results demonstrated that the interaction between SCN- and the electrode is so strong that its SERS signal can be detected in the whole research potential region (-0.1 V(-)-1.4 V). The orientation change may occur in the potential range -0.6 V-0.7 V. From -0.1 V to -0.6 V SCN- is adsorbed mainly through S end onto Au surface while in the potential range of -0.7 V to -1.2 V it is oriented mainly through N end. The potential dependence of the Raman frequency of nu CN resulted in two different values of electrochemical Stark effect, suggesting the existence of molecular orientation change.