Abstract: A catalyst‐free reductive functionalization of CO2 with amines and NaBH4 was developed. The N‐methylation of amines was carried out with CO2 as a C1 building block and 1,4‐dioxane as the solvent. Notably, the six‐electron reduction of CO2 to form the methyl group occurred simultaneously with formation of the C−N bond to give the N‐methylated amine.