The order-disorder phenomenon and spatial heterogeneity of chain packing, partitions of stereodefects, and molecular dynamics of alpha form of isotactic polypropylene (iPP) samples, which are synthesized by Zieglar-Natta catalysts, are investigated by solid-state (SS) NMR. High-resolution C-13 NMR under high-power TPPM decoupling at field strengths of 110 kHz allows observation of the order-disorder phenomenon in the chain-packing structures of alpha form. High isotacticity samples (isotacticity at Pentad level, < mmm > = 99.4%) give a maximum ordered packing (alpha(2)) fraction of 66% at crystallization temperature (T-c) of 155 degrees C while low stereoregularity samples (< mmmm > = 91.0%) have only 47% at the same T-c However, M-w (58.7-982 kg/mol) does not play a significant role in ordered packing formation. Using C-13-labeled CH3 of iPP, direct spatial correlations between the alpha(2) and alpha(1) structures are investigated by C-13 detection of two-dimensional (2D) H-1-H-1 spin-diffusion (CHHC) experiments. The time dependence of the spin-diffusion polarization transferred signal intensities determines the average domain size of the alpha(1) and alpha(2) structures of iPP crystallized at 150 degrees C, which was found to be 40 nm under an assumption of 2D spin diffusion. Additionally, the C-13 filter CPMAS NMR spectrum on C-13 CH3-labeled iPP demonstrates that chemical defect is almost excluded from the crystalline region at T-c = 150 degrees C (defect free crystal) while ca. 2% is in melt quench sample. Moreover, C-13 centerband-only detection of exchange experiments on alpha(2)-rich sample with highest < mmmm > = 99.4% indicate that crystalline dynamics follows a single Arrhenius plot with an activation energy of 116 kJ/mol across reported order-disorder transition temperatures (157-159 degrees C).