The adsorption of CO molecule on the LaCoO3 (0 0 1) surface has been investigated using density functional theory calculation. Calculation results show that the most suitable configuration is Co-CO structure for the CoO-terminated LaCoO3 (0 0 1) surface. In the adsorption process electrons transfer from CO molecule to the surface. The Co-C bond is mainly from the hybrid between the CO and Co-d orbital. When CO molecule adsorption on the LaO-terminated LaCoO3 (0 0 1) surface, the most suitable configuration is the O-CO structure and the electrons transfer from the surface to the CO molecule in the adsorption process. The bond between the C atom and the surface O atom is mainly from the hybrid between the C-2p and O-2p orbital. The LaCoO3 could be used as the gas sensing material to detect CO gas. (C) 2014 Elsevier B.V. All rights reserved.