This research investigated the synthesis of thermoplastic polyurethane (TPU) with a hard segment content (HSC) of 30% weight. The chain extender, the polyols, and the diisocyanate utilized 1,4-butanediol (BDO), and the polycaprolactone diol (PCL-diol) with molecular weights of 2000, 4000, and 10,000 and isophorone diisocyanate (IPDI), respectively. Differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (1H-NMR), and X-ray diffraction (XRD) were used to examine the chemical microstructure and physical properties of PCL diol and thermoplastic polyurethanes (TPUs). The molecular weight of the PCL diol as soft segments affected the crystallinity and glass transition temperature (Tg) of TPUs. An increase in PCL diol molecular weight resulted in a reduction in elongation at failure and an increase in ultimate tensile strength. This study was conducted to investigate the permeability and the permselectivity of CO2 and N2 gases over pressure ranges (3 to 9 atm). It was determined that the gas permeability of each sample increased in response to an increase in the pressure of the supplying gas. An elevation in the molecular weight of PCL-diols in TPU samples resulted in a reduction in selectivity and an increase in CO2 and N2 gas permeability. Although IPDI is a non-aromatic cyclic diisocyanate with a significant impact on thermoplastic polyurethane phase morphology, the goal of this paper is to create a change in the molecular weight of PCL-diol and investigate the effect of molecular weight on the resulting morphology as well. [ABSTRACT FROM AUTHOR]