The invention discloses an ultramicropore metallic organic framework material Zn(ox)0.5(mtz) as well as a preparation method and adsorption separation application thereof. The material has a structural chemical formula of Zn(ox)0.5(mtz), wherein ox is oxalic acid, mtz is 3-methyl-1H,1,2,4-triazole. The preparation method comprises the following steps: (1) weighing oxalic acid, 3-methyl-1H,1,2,4-triazole and a zinc metal salt, and uniformly mixing with water or water and alcohols; (2) adding the mixture into a high-pressure reaction kettle for reaction, filtering, and washing to obtain Zn(ox)0.5(mtz). The material has ultramicropores, and is good in water stability, preferential adsorption of carbon dioxide can be achieved, in addition, a large adsorption capacity is achieved, and meanwhile, adsorption of gases such as methane, acetylene, nitrogen, ethylene, ethane and the like is completely excluded, therefore, the material can be applied to efficient desorption of carbon dioxide impurities in multiple chemical engineering situations.