The design of an ecologically friendly and low-energy adsorption separator for acquiring high-purity n-butene (n-C 4 H 8 ) and iso-butene (i-C 4 H 8 ) has been anticipated but has not yet materialized. Here, we proposed a physical adsorbent (CALF-20) of a super cage with four-way through and window-specific shrinkage for high-efficiency molecular sieving n-C 4 H 8 and i-C 4 H 8 . Compared with other molecular sieving materials, the adsorption capacity of n-C 4 H 8 created a new benchmark (64.27, 54.82, and 0.01 bar). In situ single-crystal X-ray diffraction (SCXRD) and computational simulation validated the vital role of window-specific shrinkage and object adaptation of CALF-20 for high-efficiency molecular sieving and enhancing the n-C 4 H 8 binding interaction. Breakthrough experiments under dry and humid circumstances proved that CALF-20 can achieve efficiently purified i-C 4 H 8 (≥99.999%) with a benchmark productivity of 105 L/kg by one-step adsorption from a n-C 4 H 8 /i-C 4 H 8 (50/50, v/v) mixture. The excellent separation performance of CALF-20 provides a perfect platform for industrial separation applications.