Abstract Microporous polymer membranes continue to receive tremendous attention for energy‐efficient gas separation processes owing to their high separation performances. A new network microporous polyamide membrane with good molecular‐sieving performance for the separation of N 2 from a volatile organic compound (VOC) mixture is described. Triple‐substituted triptycene was used as the main monomer to form a fisherman's net‐shaped polymer, which readily forms a composite membrane by solution casting. This membrane exhibited outstanding separation performance and good stability for the molecular‐sieving separation of N 2 over VOCs such as cyclohexane. The rejection rate of the membrane reached 99.2 % with 2098 Barrer N 2 permeability at 24 °C under 4 kPa. This approach promotes development of microporous membranes for separation of condensable gases.