Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties. Here, remarkable acetylene/carbon dioxide separation featuring a high dynamic breakthrough capacity for acetylene (4.3 mmol·g^–1) as well as an ultralow acetylene regeneration energy (29.5 kJ·mol^–1) was achieved with the novel TiF₆^2–-pillared material ZU-100 (TIFSIX-bpy-Ni). Construction of a pore structure with abundant TiF₆^2– anion sites and pores with appropriate sizes enabled formation of acetylene clusters through hydrogen bonds and intermolecular interactions, which afforded a high acetylene capacity (8.3 mmol·g^–1) and high acetylene/carbon dioxide uptake ratio (1.9) at 298 K and 1 bar. Moreover, the NbO₅^2– anion-pillared material ZU-61 investigated for separation of acetylene/carbon dioxide. In addition, breakthrough experiments were also conducted to further confirm the excellent dynamic acetylene/carbon dioxide separation performance of ZU-100.