The synthesis of N-substituted amines is one of the key transformations in synthetic chemistry and chemical industry,because amines are ubiquitous in the syntheses of agrochemicals,pharmaceuticals,flavorings,fragrances,and advanced materials.In order to realize the clean and economic synthe-sis of N-substituted amines,several aspects should be concerned.1) The application of alkyl halides as alkylation reagents should be replaced by al-cohol and alkane;2) the employment of amines as nitrogen sources can be replaced by nitrobenzene,nitrile and ammonia;3) the application of envi-ronmentally benign and low-cost starting materials,such as CO2,HCHO,biomass resources,for the nitrogen-containing chemicals synthesis should be established;and 4) economic,green and efficient catalyst should be developed for the above transformations.In this account,we describe our results in the clean and economic synthesis of N-substituted amines with amine,ammonia,nitrobenzene or nitrile as nitrogen sources and alcohol,alkane or CO2,HCHO,CO,and biomass resources as alkylation or carbonylation reagents.