Here, we report the synthesis of spherical bimetal ZnCo-MOF materials by a hydrothermal rotacrystallization method and their catalytic activity on the air epoxidation of mixed biolefins enhanced by microwaves. The structural and chemical properties of the ZnCo-MOF materials were fully characterized by XRD, IR, SEM, TG, XPS, and NH 3 -TPD. The morphology of the material exhibited a three-dimensional spherical structure. From an NH 3 -TPD test of the ZnCo-MOF catalyst, it could be concluded that the Zn 0.1 Co 1 -MOF-H-150 rpm material had the highest acidic content and the strongest acidity among the catalysts synthesized by different methods, which gave the best performance in the epoxidation of mixed biolefins. The air epoxidation reaction was carried out under atmospheric pressure and microwave conditions, in the absence of any initiator or coreducing agent. Moreover, the Zn 0.1 Co 1 -MOF catalyst could be recycled six times without reducing the catalytic activity significantly, which showed the stability of spherical catalyst material under microwaves.