Copper oxides (CuO and Cu 2 O) semiconductor micro-and nanostructures have been selectively synthesized using cupric nitrate trihydrate (Cu(NO 3) 2 •3H 2 O), potassium biphthalate (KHC 8 H 4 O 4) and sodium hydroxide (NaOH) as starting materials in water solution by a simple hydrothermal method. The phase and morphology of the products could be controlled by changing the amount of sodium hydroxide and sodium potassium biphthalate. X-ray diffraction (XRD), field scanning electron microscopy (SEM) and Raman spectra (Raman) were used to characterize the products. It was found that oval-shaped CuO, CuO nanoplates and octahedral Cu 2 O were prepared by adjusting the molar of the NaOH and KHC 8 H 4 O 4 , meaning that NaOH and KHC 8 H 4 O 4 played an important role in the morphology and phase of the samples. The catalytic application in accelerating catalytic decomposition of ammonium perchlorate (AP) of the as-prepared samples was also investigated by means of differential scanning calorimetry (DSC). Compared with CuO (oval-shaped or plates), octahedral Cu 2 O exhibited better catalysis on thermal decomposition of AP. The present work can afford some guidance for the rationally controllable synthesis of other catalytic materials.