The present invention is synthesis process of N-aryl substituted aryl amide compound. Aryl amide and aromatic nitro compound are reacted in organic solvent inside high pressure reactor in the presence of CO with selenium as catalyst and DBU and triethylamine as co-catalyst, where, the substitutent on the aryl radical in the aromatic compound may be electron donor or acceptor group(s), the material molar ratio between aryl amide and aromatic nitro compound is 0.1-10, the molar consumption of selenium is 0.1-20 % of the less material, the molar consumption of triethylamine is 10-200 % of the less material, the molar ratio between the reactant and organic solvent is 0.02-1, the reaction period is 2-20 hr, reaction temperature is 50-200 deg.c, and CO pressure is 1-10 MPa gauge pressure. The present invention has simple operation, high selectivity, high yield, stable product quality and easy post separation.