An efficient ligand- and transition metal-free procedure for the direct Csp2O bond formation for the arylation of 2-aryl-4-quinolones was developed. The synthesis of the starting quinolones was carried out under our optimized Cu-catalyzed CN bond formation conditions between 2′-bromoacetophenone and benzamide derivatives followed by cyclization. Easily prepared diaryliodonium salts were used as aryl source. Highly functionalized 4-aryloxyquinolines were obtained in a mild and operationally simple protocol, which involves conventional heating and short periods of time. The method shows good to excellent yields and broad toleration of functional groups like fluorine or trifluoromethyl, which are important in medicinal chemistry. The Csp2O bond formation process herein described for the quinolone functionalization offers an excellent non-toxic alternative to the transition metal-catalyzed reactions that not only can potentially contaminate the final compounds but also can be environmental pollutants.