One-step separation of C ₂ H ₄ from ternary C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ hydrocarbon mixtures is of great significance in the industry but is challenging due to the similar sizes and physical properties of C ₂ H ₂ , C ₂ H ₄ , and C ₂ H ₆ . Here, we report an anion-pillared hybrid ultramicroporous material, CuTiF ₆ -TPPY, that has the ability of selective recognition of C ₂ H ₄ over C ₂ H ₂ and C ₂ H ₆ . The 4,6-connected fsc framework of CuTiF ₆ -TPPY exhibits semi–cage-like one-dimensional channels sustained by porphyrin rings and TiF ₆ ²⁻ pillars, which demonstrates the noticeably enhanced adsorption of C ₂ H ₂ and C ₂ H ₆ over C ₂ H ₄ . Dynamic breakthrough experiments confirm the direct and facile high-purity C ₂ H ₄ (>99.9%) production from a ternary gas mixture of C ₂ H ₂ /C ₂ H ₆ /C ₂ H ₄ (1/9/90, v/v/v) under ambient conditions. Computational studies and in situ infrared reveal that the porphyrin moieties with large π-surfaces form multiple van der Waals interactions with C ₂ H ₆ ; meanwhile, the polar TiF ₆ ²⁻ pillars form C–H•••F hydrogen bonding with C ₂ H ₂ . In contrast, the recognition sites for C ₂ H ₄ in the framework are less marked.