The chemical conversion of carbon dioxide ( $$\hbox {CO}_2$$ CO 2 ) has been intensively studied because the molecule is responsible for global warming. Rational design of catalysts plays an important role in converting $$\hbox {CO}_2$$ CO 2 into value-added compounds. Understanding the interaction between $$\hbox {CO}_2$$ CO 2 and surfaces of catalysts is a prerequisite to preparing high-performance catalysts. This review focuses on the investigations of $$\hbox {CO}_2$$ CO 2 molecules on single crystalline surfaces studied by low-temperature scanning tunneling microscopy. Molecular adsorption, diffusion, and conversion on metal surfaces, metal oxide surfaces, and surfaces decorated by metal-organic frameworks are summarized.