The chemical conversion of carbon dioxide (CO2) has been intensively studied because the molecule is responsible for global warming. Rational design of catalysts plays an important role in converting CO2 into value-added compounds. Understanding the interaction between CO2 and surfaces of catalysts is a prerequisite to preparing high-performance catalysts. This review focuses on the investigations of CO2 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.