The invention discloses a treatment method of residues from a nitrotoluene rectification kettle. The method comprises the following steps: performing a hydrogenation reduction reaction on the residues from the rectification kettle and hydrogen in the presence of a catalyst, thereby generating methylaniline comprising three isomers, namely, o-toluidine, m-toluidine and p-toluidine, from the mononitrotoluene in the kettle residues and generating diaminotoluene comprising two isomerides, namely, 2,4-diaminotoluene and 2,6-diaminotoluene, from the dinitrotoluene in the kettle residues; and then performing rectification separation, thereby obtaining a methylaniline finished-product and a diaminotoluene finished-product. The method is simple in process, short in procedure, clean and environment-friendly, and realizes the rational utilization of waste resources, i.e., the products with high additional values are produced by utilizing low-value resources, thereby bringing economic benefits to enterprises. As a result, the recycling of waste materials, the energy conservation and the emission reduction are realized.