In this paper, Cu ions were introduced in MOF-74-Co to prepare a series of bimetallic MOF-74-Co/Cu via solvothermal method. The prepared MOFs samples were characterized by SEM, XRD, ICP-MS, TGA, and XPS in detail and their toluene adsorption capacities were tested. The results indicate when the ratio of Co/Cu is 0.68/0.32, the prepared sample of MOF-74-Co/Cu-2 displays higher toluene adsorption capacity than other samples obviously. The toluene adsorption mechanisms in MOF-74-Co/Cu are further discussed via combining EDS, XPS, FT-IR and BET characterization data with toluene adsorption isotherm analysis. Simultaneously, Freundlich adsorption isothermal model can describe the toluene adsorption behavior of MOF-74-Co/Cu better than Langmuir model. The introduction of Cu ions can increase the specific surface area and pore volume of MOF-74-Co to improve the porous structure. Moreover, Cu ions can be looked as Lewis acid to act as efficient metal adsorptive sites to enhance the capacities of toluene adsorption. The process of toluene adsorption in MOF-74-Co/Cu includes physical and chemical adsorption.