Microwave pyrolysis inherited the molecular-level engineering design of the CuCe-MOF: The tandem microwave pyrolysis firstly carbonized them to CuCe/C with topological structure, and improved the microwave absorption of MOFs in nitrogen atmosphere. Subsequently, CuCeO x catalyst was synthesized by its self-heating source of microwave in air, which endowed with molecular-level dispersed active sites to enhance preferential CO oxidation in H 2 -rich stream. • MOFs derivatives are achieved via tandem microwave pyrolysis. • Microwave pyrolysis inhibits the agglomeration of metal nanoclusters. • The tandem strategy solves the problem of poor microwave adsorption of MOFs. • Ligand carbonization provides dispersed heating sources by enhancing microwave absorption. • Microwave pyrolysis-engineered CuCeO x exhibits an outstanding performance of preferential CO oxidation. The versatile metal–organic framework (MOF) derivatives are achieved via microwave pyrolysis. The dipole vibration thermogenesis of molecules by microwave pyrolysis overcomes the issues of high energy consumption, slow heating rate, unregulated at the molecular-level, metal nanoclusters particles migration and coalescence caused by traditional thermal pyrolysis. For solving the poor microwave absorption of MOFs, a tandem microwave pyrolysis strategy is employed herein. Ligand carbonization enhances the conduction loss of microwaves and becomes a highly dispersed microwave heating source, which effectively inhibits the agglomeration. The CuCeO x catalysts obtained through this strategy retain the merits of bimetallic CuCe-MOFs with highly dispersed active species, and exhibit outstanding catalytic activities with the 100% conversion of CO being achieved at 75 °C for the preferential CO oxidation in H 2 -rich stream. These results demonstrate that the microwave pyrolysis-engineered MOFs uniformity has established catalyst with highly dispersed active species.