Cabbage-type morphology of cupric oxide (CuO) and cuprous oxide (Cu2O) nanostructures were synthesized via a simple and cost-effective chemical approach. HRTEM, FESEM, XRD, UV-Vis absorption and photoluminescence spectroscopies were used to identify the structural, optical, morphological and catalytic properties of the prepared nanostructures. Phase of the prepared copper oxide nanostructures was well controlled by changing the concentration of glucose. The prepared cabbage-type Cu2O nanostructures showed exceptionally improved catalytic performance towards the reduction of toxic 4-nitrophenol into useful 4-aminophenol as compared to cabbage-type CuO nanostructures. Cabbage-type Cu2O nanostructures completely transformed 4-NP into 4-AP in just 5min with excellent rate constant (0.587min(-1)). The observed excellent catalytic activity of prepared cabbage-type Cu2O nanostructures indicates their potential use in catalytic applications. [GRAPHICS] .