A new copper-mediated cross-coupling of arenes and arylboronic acids is described. Under the influence of Cu(OCOCF3)(2), the C-H bond arylation of electron-rich arenes with arylboronic acids takes place to afford a range of biaryis in good yields. The reaction is selective for cross-coupling; no homocoupling product arising from arenes or arylboronic acids is detected. Multiple C-H bond arylation is possible with indoles and pyrroles furnishing interesting extended pi-systems.