Multinuclear (H-1, C-13, Al-27) high-resolution solid-state nuclear magnetic resonance (NMR) during the continuous-flow of propene monomer was applied to analyze in-situ propene polymerization on Ziegler-Natta catalysts. A supported Ziegler catalyst activated with triethylaluminum and AA-TiCl3 were employed as catalysts. The time-dependent change in the spectral peak intensities during the propene polymerization with both catalysts was measured using C-13 CP MAS (cross-polarization with magic angle spinning) NMR and H-1 MAS NMR. The states of the aluminum complex in the catalysts were studied using Al-27 MAS NMR, which is sensitive to the coordination and symmetry of the local environment around the aluminum nuclei. Peculiarities of the polymerization kinetics, the crystalline states of the nascent polypropene formed on the catalyst surface, and the state of aluminum coordination and environment during the early stage of the propene polymerization under continuous-flow condition are discussed.