A copper-catalyzed 1,2-difunctionalization of ynamides has been developed by using readily available N,O-acetals as the bifunctional reagents. Importantly, contrary to the initially expected 1,2-oxy-aminomethylation reaction, an unprecedented 1,2-amino-oxymethylation has been observed. This reaction is atom-economical and tolerates a broad substrate scope, affording the difunctionalization products in good yield with unique Z configuration.