Carbon dioxide is regarded as a reliable C1 building block in organic synthesis because of the nontoxic, abundant, and economical characteristics of carbon dioxide. In this manuscript, a commercially available oxovanadium(V) compound was demonstrated to serve as an efficient catalyst for the catalytic amination of carbon dioxide under ambient pressure in the synthesis of ureas. The catalytic transformation of chiral amines into the corresponding chiral ureas without loss of chirality was also performed. Furthermore, a gram-scale catalytic urea synthesis under ambient pressure was successfully achieved to validate the scalability of this catalytic activation of carbon dioxide.