An efficient and general protocol for intermolecular C-N and C-O cross-coupling of amines, alcohols, and phenols with halides has been developed by using AgNO3 as the catalyst and N,N-dimethylethylenediamine (N,N-DMEDA) as a ligand with KOtBu as a base in a nitrogen atmosphere. A number of primary, secondary, and heterocyclic amines were coupled with various aryl iodides to give N-arylated motifs in good to excellent yield. Along with this, several substituted phenols as well as alcohols were coupled with various halides under the same reactions condition to give O-arylated compounds. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.