The cross-coupling of N,N-dialkyl aniline and aminonaphthalenes with phenols and naphthols using a Cr-salen catalyst under aerobic conditions was developed. Notably, air serves as an effective oxidant affording products in high selectivity. Initial mechanistic studies suggest an outer-sphere oxidation of the aniline/aminonaphthalene partner, followed by nucleophilic attack of the phenol/naphthol. Single products were observed in most cases, whereas mixtures of C-C and C-O coupled products arose from reactions involving aminonapthalene and sterically unencumbered phenols.