Abstract Bridging homogeneous and heterogeneous catalysis is a long-term pursuit in the field of catalysis. Herein, we report our results in integration of nano- and molecular catalysis via catalytic synthesis of nitrogen doped carbon layers on AlOx supported nano-Cu which can finely tune the catalytic performance of the supported copper catalyst. This synthetic catalytic material, which can be generated in situ by the reaction of CuAlOx and 1,10-Phen in the presence of hydrogen, could be used for controllable synthesis of N,N-dimethylformamide (DMF) from dimethylamine and CO 2 /H 2 via blocking reaction pathways of further catalytic hydrogenation of DMF to N(CH 3 ) 3 . Detailed characterizations and DFT calculations reveal that the presence of N-doped layered carbon on the surface of the nano-Cu particles results in higher activation energy barriers during the conversion of DMF to N(CH 3 ) 3 . Our primary results could promote merging of homogeneous catalysis and heterogeneous catalysis and CO 2 recycling.