A copper-catalyzed one-pot amine-alkylation of quinones with amines and alkanes in the presence of di-tert-butyl peroxide (DTBP) was developed via a radical reaction process. Various alkanes and aromatic or aliphatic amines with diverse structures and electronic properties are suitable substrates, and the chirality of amines can be maintained for the transformation. This method has high step and atom economy for straightforward access to aminated and alkylated quinones from readily available starting materials.