The catalyst for formic acid decomposition is prepared by co-precipitation method. The influence of various operation condition on catalyst activity is discussed, including precipitation, aging, auxiliary and calcination. The results of the experiment show that when multiple Ni/NiO/ZnO catalyst, which is prepared with alcohol-water solution as solvent, nickel-zinc molar ratio of 1∶1.5(mol), citric acid as the auxiliary, precipitation temperature of 60℃, aging for 4h and calcined for 4h at 500℃ in N₂, is used for formic acid decomposition in low concentration of formic acid-DMF solution, the decomposition rate is up to 95.34%.The characteristic results by XRD show that the prepared catalyst is Ni/NiO/ZnO multiple catalyst with average size of 40nm. The catalyst can be used for formic acid decomposition in recycing DMF from leather wastewater.