The adsorption of CO at polycrystalline copper surface was investigated spectroscopically. It was found that CO adsorbed as a linear adsorbed CO, Cu-COL and was a dominant species on copper surface at low CO concentration. A Cu-COL was electrochemically converted to a bridge bonded CO, Cu-COB at a high CO concentration condition. Increasing the CO surface coverage, qCO will increase the formation of adsorbed bridge bonded CO. A nitrogen gas purging treatment was used to examine the stability of an adsorbed CO through the evacuation process. The result showed that Cu-COB remained intact while Cu-COL was completely removed from the copper surface. It suggests that Cu-COL may involve in a weak bonding to a copper surface such as in a physisorbed interaction, while Cu-COB consists much stronger bonding such as a chemisorbed interaction. The N2 purging treatment also gave an additional prove that Cu-COB was partly converted to Cu(I)-CO at anodic potential regions.