The effects of nitrogen ligands as pyridine, methylpyridine, 2, 2'-bipyridine and ethylenediamine on the activity and stability of the CBAC supported copper catalyst were investigated. The catalytic activities prepared by nitrogen ligand pretreatment descended compared with the unpretreated support catalysts. This probably related to the disfavored effect of the coordination on the catalysts at the gas-solid reaction manner. The catalysts made by pyridine pretreatment and pore modified supports were superior to the catalysts of unmodified CBAC. Methanol conversion, DMC selectivity and the space-time-yield of DMC of the catalysts by HCl, pyridine pretreatment and pore modification were 28.3%, 97.3% and 165.3 g/(kg•h), respectively. Activity test of 30h showed that pyridine pretreatment can prevent the loss of the active component and enhance the stability of the catalysts.