Adsorption and orientation of ethyl xanthate on a copper electrode was studied using an in situ spectroelectrochemical set up. Cuprous xanthate was identified to be the major product over the potential range - 0.5 to - 0.1 V (SCE). A further increase in electrode potential to 0.1 V resulted in the formation of dixanthogen in addition to cuprous xanthate. The characteristic dixanthogen bands disappeared and the intensity of cuprous xanthate bands increased when the potential was brought back and held at -1.0 V. With polarized radiation, the spectral appearance of cuprous xanthate changed in contrast to that of dixanthogen, suggesting preferential orientation of cuprous xanthate molecules but random orientation for dixanthogen.