The invention belongs to the field of pharmaceutical chemistry, and provides a preparation method of an asenapine key impurity (IV) trans-5-chloro-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole. The trans-5-chloro-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole is prepared from trans-5-chloro-2,3,3a,12b-tetrahydro-2-methyl-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole used as the initial raw material. The impurity is a very key impurity for synthesizing asenapine, and is also an important intermediate for controlling the asenapine end product quality standard.