Aryl(triethyl) silanes were found to cross-couple with aryl chlorides by palladium/copper dual catalysis and XPhos as a crucial ligand. The catalyst system is applicable to a facile oligothiophene synthesis from thienyl(trialkyl) silanes and thienyl chlorides. As the starting silanes are readily accessible by the catalytic C-H silylation, our method provides a protocol for a rapid biaryl synthesis starting with aromatic hydrocarbons straightforwardly.