Biomass‐derived furfural was used as a CO surrogate for the first time in the oxidative N‐dealkylation/carbonylation of various aliphatic and cyclic tertiary amines with terminal alkynes to produce alk‐2‐ynamides. This reaction employed O2 as an ideal oxidising agent and used a Pd/C catalyst with KI as an additive in a base free and ligand free condition. Notably, the selective sp3 C‐N bond cleavage of tertiary amines led to its potential application as an amine source. The typical and simple route provides another option for producing a broad variety of alk‐2‐ynamide derivatives in environmentally friendly and efficient way under mild conditions. This method also displays notable reusability.