The catalytic reduction of carbon dioxide to carbon monoxide under mild conditions using aromatic aldehydes as reductants and NHCs as organocatalysts was developed. This carbon dioxide splitting reaction provides a new method for metal-free carbon dioxide reduction and steps forward in utilizing carbon dioxide as a renewable “green” source under mild conditions. On the other hand, this reaction also shows a new economical way to oxidize aromatic aldehydes under mild conditions with carbon dioxide and could be applied in pharmaceutical synthesis.