The invention discloses a palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds, relating to a nitrification method, comprising the following steps: successively adding the aza calixarene compounds, palladium catalyst, nitrated reagent, oxidizing agent and reaction solvent in a sealed pressure container, controlling the pressure between 1 mbar and 100 bar, heatingthe mixture for 6-72 hour in an oil bath with the reaction temperature of 30-200 DEG C to obtain a product of the ortho-orientation nitrification. According to the invention, the method is carried out under neutral conditions, and has no generation of exhaust gas and waste water; directional mononitration is only carried out on the ortho-position of the nitrogen containing substituents without being influenced from other substituents on aromatic nucleus, and the chemo-selectivity and region-selectivity are good; the functional groups and the substrate have good adaptability, and the directional ortho-position nitration of a plurality of aromatic nucleus containing various substituents and a plurality of aromatic nucleus containing various nitrogen containing oriented groups can all be realized; and pre-functionalized aromatic compounds are not needed.