To address the inherent limitations of current MOF synthesis, where pore size is restricted to micropores or small mesopores, we successfully synthesized MOF composite materials with well-developed porous structures using a self-template approach. These pores encompass not only the intrinsic micropores or small mesopores of MOFs but also the template-induced large pores. During the experimental process, we achieved the synthesis of composite materials with varying MOF contents by modifying experimental conditions. Through this design, we not only achieved selective adsorption of guest molecules but also significantly increased the porosity, thereby enhancing the mass transfer efficiency of guest molecules and the utilization rate of materials. This research breakthrough offers new insights and solutions for addressing critical issues in fields such as gas separation, energy storage, and catalysis.