The invention relates to a metallic organic frame material based on a YbIII pentanuclear molecular structure unit, a preparation method and an application thereof. According to the technical scheme, the method comprises the following steps: adding Yb(NO3)3, ligand 5,5'-(4-carboxyl-pyridyl-2,5-bis-substituted)-1,3-phthalic acid, solvent N,N-dimethyl formamide and water into a high-temperature resisting spiral opening glass bottle; stirring for 30 minutes under normal temperature; sealing the container and then putting into an oven; keeping for 4 days under the temperature at 378K; slowly cooling to room temperature, thereby acquiring a colorless transparent block crystal; washing with N,N-dimethyl formamide, filtering and drying, thereby acquiring a target product. The metallic organic frame material based on the YbIII pentanuclear molecular structure unit prepared according to the invention is simple in preparation method and has an excellent size selective catalytic performance for the carbon dioxide cycloaddition reaction of the epoxide.