We synthesized a series of rigid ladder-type diamines from readily available bromoanilines and norbornadiene in one step using facile catalytic arene-norbornene annulation (CANAL). Polycondensation of CANAL ladder diamines with 4,4’-(hexafluoroisopropylidene) diphthalic anhydride led to a series of microporous polyimides with different degrees of rotational freedom around the imide linkages. These CANAL-PIs exhibited good solubility in a wide range of organic solvents, high thermal stability with decomposition temperature above 450 °C, high Brunauer-Emmett-Teller sur-face areas of ~ 200 – 530 m2 g-1, and abundant micropore volume with variable pore size distributions. Mechanically robust membranes can be easily formed from these CANAL-PIs and gave high gas permeabilities and moderate gas-pair selectivities. CANAL-PIs had higher permeability and similar permselectivity compared to analogous PIs synthe-sized from Tröger’s base and carbocyclic Tröger’s base diamines under identical test conditions. CANAL-PIs also exhibited relatively slow physical aging. These favorable properties and performance make microporous polymers based on CANAL ladder motifs promising membrane materials for important gas separation.