Cacotheline was identified as a highly effective organocatalyst for the aerobic oxidation of amines either without solvent or in water. The facile redox properties of cacotheline allowed the aerobic oxidation of amines to imines at 23 °C and to aldehydes at 80 °C, respectively. The low catalyst loading combined with the ready separation of products in high purity without further purification steps demonstrates a greener and more sustainable approach to aerobic amine oxidation chemistry.