A straightforward Cu(I)-catalyzed oxidative cross-coupled organic transformation has been developed under mild conditions for the construction of functionalized 4,5-dihydrooxazoles through a four-bond-forming regiocontrolled C-C/C-N/C-O coupling strategy emerging benzimidates, paraformaldehyde, and 1,3-diketo analogues using eco-friendly O2 as the sole oxidant. The fundamental features of these designed approaches involve operational simplicity, selectivity, generality, and a broad substrate scope with high yields under the same reaction conditions.