In this study, triptycene-based carboxylic acid (triptycene-2,3,6,7-tetracarboxylic acid) was synthesized for polycondensation with two amino compounds to ultimately form linear polyamides with different backbone structures. Characterizations, including nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy, were performed to confirm the poly -condensation, and the structural properties were determined. Solubility of the synthesized polyamides was also measured. Subsequently, these polyamides were fabricated into membranes to investigate the separation of N2 over the VOCs, and their stability and separation performance under different operating conditions were de-termined. Good separation performance, such as a rejection rate above 95%, was obtained during the studied separation range for the N2/VOC mixture, indicating that a linear polymer can also be used for the separation of a condensable gas/vapor mixture and only the rotation of polymer chains can be restricted to a certain extent by the side groups. Superscript/Subscript Available