Separation of methane (CH4) from other gases is of significant importance to reducing greenhouse gas emissions. In particular, the development and discovery of efficient adsorbents under pressure swing adsorption (PSA) conditions is a focus many research papers. We evaluated the potential of CH4/N2 separation performance using four adsorbents, including zirconium-based metal organic frameworks (NU-1000, UiO-66, and UiO-67) and a conventional adsorbent, zeolite-13X. Among them, NU-1000 presented high CH4/N2 selectivity (2.8) at 15 bar through ideal adsorbed solution theory because it has micro- and mesopores coupled with the large surface area, and a polar hydroxyl group along the pore surface. NU-1000 has a large CH4 working capacity (4.79) under PSA processes. These results demonstrated that NU-1000 is a sufficiently competitive adsorbent in PSA processes for CH4/N2 separation.