Abstract Buchwald precatalyst (XantPhos Pd-G3) was employed for the first time in a C–S cross-coupling reaction involving 2-(4-bromophenyl)benzothiazole or 5-bromo-2,1,3-benzothiadiazole with various benzenethiols in DMF, K2CO3 as a base, under microwave irradiation at 80 °C, 200 W. Good to excellent yields of the desired products were obtained under microwave conditions. Other significant benefits of this synthetic approach are low catalyst loading, short reaction times, and eco-friendly conditions. Additionally, 29 compounds were successfully synthesized, some of which are new in this protocol.