A series of N- substituted polyether- block -amide (PEBA-X%) copolymers were prepared by melt polycondensation of nylon-6 prepolymer and polytetramethylene ether glycol at an elevated temperature using titanium isopropoxide as a catalyst. The structure, thermal properties, and crystallinity of PEBA-X% were investigated using nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry, wide angle X-ray diffraction, and thermogravimetric analysis. In general, the crystallinity, melting point, and thermal degradation temperature of PEBA-X% decreased as the incorporation of N -methyl functionalized groups increased, owing to the disruption caused to the structural regularity of the copolymer. However, in N -acetyl functionalized analogues, the crystallinity first dropped and then increased because of a new γ form arrangement that developed in the microstructure. After the cross-linking reaction of the N -methyl-substituted derivative, which has electron-donating characteristics, with poly(4,4′-methylenebis(phenyl isocyanate), the decomposition temperature of the resulting polymer significantly increased, whereas no such improvements could be observed in the case of the electro-withdrawing N -acetyl-substituted derivative, because of the incompleteness of its cross-linking reaction.