We present adirect cross-coupling reaction between arylaluminum compounds (ArAlMe 2 ·LiCl) and organic halides RX (R = aryl, alkenyl, alkynyl;X=I, Br,and Cl) without any external catalyst. The reaction takes place smoothly,simply upon heating, therebye nabling the efficient and chemo-/ stereoselective formation of biaryl, alkene,a nd alkyne coupling products with broad functional group compatibility.