8-chlorodibenzo[b,f]thiepin-10(11H)-one, a key synthetic intermediate of Zotepine, was synthesis by metal-catalyzed coupling reaction, Willgerodt-Kindler rearrangement, hydrolysis and intermolecular cyclization reaction. The coupling reaction was catalyzed by CuI/L-proline, reaction temprature could be cooled down to 100 oC with a higher yield, 85%. Willgerodt-Kindler rearrangement and hydrolysis was carried out in a one-pot-reaction. The mole yield of all four steps is 40%. Product structure was identified by IR, Ms, and H 1NMR.